CN106935664A

CN106935664A - Passivation layer is formed with composition, semiconductor substrate and manufacture method, solar cell device and manufacture method, solar cell

Info

Publication number: CN106935664A
Application number: CN201611001547.9A
Authority: CN
Inventors: 足立修郎; 足立修一郎; 吉田诚人; 野尻刚; 仓田靖; 田中彻; 织田明博; 早坂刚
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Resonac Corp
Priority date: 2012-07-12
Filing date: 2013-07-12
Publication date: 2017-07-07
Also published as: KR20150036286A; TW201412761A; CN104471715A; CN104471715B; TWI615395B; WO2014010743A1; JPWO2014010743A1

Abstract

Passivation layer formation of the invention composition comprising the organo-aluminum compound shown in following logical formula (I)s and selected from titanium alkoxide, zirconium alkoxides and silicon alkoxide at least one alkanol salt compound.In following logical formula (I)s, R¹Separately represent the alkyl of carbon number 1~8；N represents 0~3 integer；X²And X³Separately represent oxygen atom or methylene；R²、R³And R⁴Separately represent the alkyl of hydrogen atom or carbon number 1~8.

Description

Passivation layer is formed with composition, semiconductor substrate and manufacture method, solar cell unit Part and manufacture method, solar cell

The application is that applicant submits in July 12 2013 applying date, international application no is PCT/JP2013/ 069222nd, into National Phase in China Application No. 201380036883.5, entitled " passivation layer formation combination Thing, the semiconductor substrate with passivation layer and its manufacture method, solar cell device and its manufacture method and solar-electricity The divisional application of the application for a patent for invention in pond ".

Technical field

The present invention relates to passivation layer formation composition, the semiconductor substrate with passivation layer and its manufacture method, solar energy Cell device and its manufacture method and solar cell.

Background technology

Manufacturing process to conventional silicon solar cell element illustrates.

First, high efficiency is realized in order to promote sunken luminous effect, preparation is formed with the p-type of texture structure in light surface side Silicon substrate, then, in phosphorous oxychloride (POCl₃), nitrogen, enter line number at 800 DEG C~900 DEG C in the mixed-gas atmosphere of oxygen The treatment of ten minutes, is formed uniformly n-type diffusion layer.

In the conventional method, due to carrying out the diffusion of phosphorus using mixed gas, therefore not only on the surface of smooth surface N-type diffusion layer is formed, and n-type diffusion layer is also formed in side and the back side.Therefore, the N-shaped that side is formed to remove expands Dissipate layer and carry out lateral erosion.Additionally, the n-type diffusion layer for being formed at the back side needs to be transformed to p⁺Type diffusion layer.Therefore, entirely carrying on the back Aluminum Paste of the face coating comprising aluminium powder and adhesive is simultaneously heat-treated (burn till) to it and is formed aluminium electrode, thus makes N-shaped Diffusion layer turns into p⁺Type diffusion layer, while obtaining Ohmic contact.

But, the electrical conductivity of the aluminium electrode formed by Aluminum Paste is low.Therefore, in order to reduce film resistor, it is generally formed in The aluminium electrode at the whole back side must have 10 μm~20 μm or so of thickness after (burning till) is heat-treated.And then, due to silicon and aluminium Coefficient of thermal expansion differ widely, therefore, during heat treatment (burning till) and cooling, be formed with product in the silicon substrate of aluminium electrode The larger internal stress of life, so as to cause grain boundary damage (damage), crystal defect to increase and warpage.

In order to solve the problem, it is reduced the coating weight of Aluminum Paste and makes the thinning method of the thickness of back electrode layer.But It is, if reducing the coating weight of Aluminum Paste, to become not fill from the diffusion into the surface of p-type silicon semiconductor substrate to internal aluminum amount Point.As a result：BSF (Back Surface Field, back surface field) effect needed for cannot realizing is (because of p⁺The presence of type diffusion layer and make Generate the effect that the collection efficiency of carrier is improved), therefore produce the problem of the characteristic reduction of solar cell.

Based on above-mentioned situation, it is proposed that be formed locally p by assigning Aluminum Paste in a part for silicon substrate⁺Type The method (referring for example to No. 3107287 publications of Japanese Patent No.) of the point contact of diffusion layer and aluminium electrode.

It is this kind of the side (hereinafter also referred to " rear side ") opposite with smooth surface have point-contact junction structure solar-electricity , it is necessary to suppress the recombination velocity of minority carrier on the surface of the part in addition to aluminium electrode in the case of pond.As being used for The passivation layer (hereinafter also referred to as " passivation layer ") of the rear side of the purposes, it is proposed that SiO₂Film etc. is (referring for example to Japanese special Open 2004-6565 publications).As because forming the passivation effect produced by this kind of oxide-film, including by the back gauge of silicon substrate The silicon atom in layer portion uncombined key end-blocking so that cause in conjunction with surface energy level density reduction effect.

Additionally, as suppress minority carrier in conjunction with other methods, using the fixed charge in passivation layer Produced electric field is come the method that reduces minority carrier density.Such passivation effect is commonly known as field effect, and carries Aluminum oxide (Al is gone out₂O₃) film etc. as the material with negative fixed charge (referring for example to No. 4767110 public affairs of Japanese Patent No. Report).

Such passivation layer generally passes through ALD (Atomic Layer Deposition, ald) methods or CVD The methods such as (Chemical Vapor Depositon, chemical vapor deposition) method are formed (referring for example to Journal of Applied Physics, 104 (2008), 113703-1~113703-7.).Additionally, conduct is formed on a semiconductor substrate The easy method of pellumina, it is proposed that using the method for sol-gal process (referring for example to Thin Solid Films, 517 (2009), 6327-6330 and Chinese Physics Letters, 26 (2009), 088102-1~088102-4.).

On the other hand, if forming refractive index greatly and the also big layer of passivation effect in the light surface side of silicon substrate, can press down System falls into the raising of luminous effect and the recombination velocity of minority carrier, and can improve the generating efficiency of solar cell.Example Such as propose the refractive index that the oxide-film for making titanium metal and the compound gained of aluminium is formed by using sol-gal process to increase film Method (referring for example to Japanese Journal of Applied Physics, 45 (2006), 5894~5901.).

The content of the invention

The invention problem to be solved

Journal of Applied Physics, 104 (2008), the method described in 113703-1~113703-7. Comprising the manufacturing process that evaporation etc. is complicated, so in the presence of being difficult to put forward large-duty situation.Additionally, for Thin Solid Films, 517 (2009), 6327~6330. and Chinese Physics Letters, 26 (2009), 088102-1~ In the passivation layer formation composition of the method described in 088102-4., with understanding time dependent a problem that generation gelation, protect Stability is deposited also to be difficult to deserve to be called abundant.And then, for by Japanese Journal of Applied Physics, 45 (2006), for the passivation layer that the method described in 5894~5901. is obtained, its refractive index is also difficult to deserve to be called fully big, deposits In the worry of the photocatalysis from titanium oxide, the sealing resin of solar cell device may be assigned and damaged.

The present invention in view of the conventional problem of the above and complete, its problem is needed for providing and being formed in easy method The passivation layer formation composition of shape and the fully big passivation layer of refractive index and excellent storage stability.Additionally, of the invention Problem also reside in provide and have the band using the fully big passivation layer of obtained by the passivation layer formation composition, refractive index blunt Change the semiconductor substrate and its manufacture method, solar cell device and its manufacture method and solar cell of layer.

Means for solving the problems

Specific means for solving above-mentioned problem is as described below.

A kind of passivation layer formation compositions of the ＞ of ＜ 1, it includes the organo-aluminum compound shown in following logical formula (I)s and is selected from At least one alkanol salt compound in titanium alkoxide, zirconium alkoxides and silicon alkoxide.

【Change 1】

[in logical formula (I), R¹Separately represent the alkyl of carbon number 1~8.N represents 0~3 integer.X²And X³It is only respectively On the spot represent oxygen atom or methylene.R²、R³And R⁴Separately represent the alkyl of hydrogen atom or carbon number 1~8.]

Passivation layer formation compositions of the ＞ of ＜ 2 according to the ＞ of ＜ 1, it also includes alkanol niobium.

Passivation layer formation compositions of the ＞ of ＜ 3 according to the ＞ of ＜ 2, wherein, above-mentioned alkanol niobium is selected from ethanol niobium, different At least one in propyl alcohol niobium, normal propyl alcohol niobium, n-butanol niobium and phenol niobium.

Passivation layer formation compositions of the ＞ of ＜ 4 according to any one of the ＞ of 1 ＞ of ＜~＜ 3, wherein, above-mentioned alkoxide Compound comprises at least above-mentioned titanium alkoxide, and above-mentioned titanium alkoxide is selected from methyl alcohol titanium, titanium ethanolate, isopropyl titanate, normal propyl alcohol titanium, positive fourth In alcohol titanium, tert-butyl alcohol titanium, titanium isobutoxide, diisopropoxy bis-acetylacetonate titanium and four (2- ethyl -1- hexanols) titaniums at least It is a kind of.

Passivation layer formation compositions of the ＞ of ＜ 5 according to any one of the ＞ of 1 ＞ of ＜~＜ 4, wherein, above-mentioned alkoxide Compound comprises at least above-mentioned zirconium alkoxides, and above-mentioned zirconium alkoxides are selected from ethanol zirconium, zirconium iso-propoxide, zirconium-n-propylate, zirconium-n-butylate, uncle At least one in butanol zirconium, acetylacetone,2,4-pentanedione zirconium, trifluoroacetylacetone (TFA) zirconium and hexafluoroacetylacetone zirconium.

Passivation layer formation compositions of the ＞ of ＜ 6 according to any one of the ＞ of 1 ＞ of ＜~＜ 5, wherein, above-mentioned alkoxide Compound comprises at least above-mentioned silicon alkoxide, and above-mentioned silicon alkoxide is the silicon alkoxide shown in following logical formula (II)s.

(R⁵O)_(4-m)SiR⁶ _m (II)

[in logical formula (II), R⁵And R⁶Separately represent the alkyl of carbon number 1~8.M represents 0~3 integer.]

Passivation layer formation compositions of the ＞ of ＜ 7 according to any one of the ＞ of 1 ＞ of ＜~＜ 6, it also includes resin.

Passivation layer formation compositions of the ＞ of ＜ 8 according to any one of the ＞ of 1 ＞ of ＜~＜ 7, it is also comprising following logical Compound shown in formula (III).

【Change 2】

A kind of semiconductor substrates with passivation layer of the ＞ of ＜ 9, it has semiconductor substrate and is arranged at above-mentioned semiconductor substrate On whole face or a part passivation layer, the passivation layer be the ＞ of 1 ＞ of ＜~＜ 8 any one of passivation layer formation group The heat treatment thing of compound.

A kind of manufacture methods of the semiconductor substrate with passivation layer of the ＞ of ＜ 10, it includes：To the whole face on semiconductor substrate Or a part assigns the passivation layer formation composition any one of ＜ 1 ＞~＞ of ＜ 8 and forms the operation of composition layer； The operation of passivation layer is formed with being heat-treated to combinations thereof nitride layer.

A kind of solar cell devices of the ＞ of ＜ 11, it has：P-type layer and n-layer are carried out the semiconductor of pn engagements Substrate；The whole face being arranged on above-mentioned semiconductor substrate or the passivation layer of a part, the passivation layer is in the ＞ of 1 ＞ of ＜~＜ 8 The heat treatment thing of the passivation layer formation composition described in any one；Be configured at above-mentioned semiconductor substrate selected from above-mentioned p-type The electrode on the layer of more than 1 in layer and n-layer.

A kind of manufacture methods of solar cell device of the ＞ of ＜ 12, it includes：To with by p-type layer and n-layer engagement Into pn-junction and more than 1 in selected from above-mentioned p-type layer and above-mentioned n-layer layer on have electrode it is semiconductor substrate, At least a portion in the face with above-mentioned electrode, assigns the passivation layer formation composition any one of 1 ＞ of ＜~＞ of ＜ 8 And form the operation of composition layer；The operation of passivation layer is formed with being heat-treated to combinations thereof nitride layer.

A kind of solar cells of the ＞ of ＜ 13, it has solar cell device described in the ＞ of ＜ 11 and is configured at the above-mentioned sun Wiring material on the electrode of energy cell device.

Invention effect

According to the present invention it is possible to providing required shape and the fully big passivation of refractive index can be formed in easy method The passivation layer formation composition of layer and excellent storage stability.Additionally, being used it is also possible according to the present invention to provide having The semiconductor substrate with passivation layer of the fully big passivation layer of obtained by the passivation layer formation composition, refractive index and its manufacture Method, solar cell device and its manufacture method and solar cell.

Brief description of the drawings

(d) of (a) of Fig. 1~Fig. 1 is the sun with passivation layer for schematically showing an embodiment of the invention The sectional view of of the manufacture method of energy cell device.

(e) of (a) of Fig. 2~Fig. 2 is the sun with passivation layer for schematically showing an embodiment of the invention The sectional view of another of the manufacture method of energy cell device.

Fig. 3 is the back electrode type solar cell with passivation layer for schematically showing an embodiment of the invention The sectional view of element.

Specific embodiment

In this manual, term " operation " is not only independent operation, but also has and cannot clearly be different from other works The situation of sequence, as long as can realize the purpose of the operation in this case, is then also contained in this term.Additionally, using "~" to show The number range for going out represents the numerical value of the front and rear record containing "~" respectively as minimum value and the scope of maximum.And then, close The content of each composition in composition, in the case of there are various materials equivalent to each composition in the composition, as long as not having There is special instruction, then each mean the total amount of many kinds of substance present in composition.Additionally, term " layer " in this manual In addition to the composition comprising the shape for being formed at whole face when observing in top plan view, also comprising seeing in top plan view The composition of the shape of a part is formed at when examining.

＜ passivation layers are formed and use composition ＞

Passivation layer formation composition of the invention (is also referred to as below comprising the organo-aluminum compound shown in following logical formula (I)s Make " specific organo-aluminum compound ") and selected from titanium alkoxide, zirconium alkoxides and silicon alkoxide at least one alkanol salt compound (with Down also referred to as " specific alkanol salt compound ").Above-mentioned passivation layer formation composition can also as needed comprising other into Point.Specific organo-aluminum compound and specific alkanol salt compound are included by making passivation layer formation composition, so as to It is enough to form required shape and the fully big passivation layer of refractive index in easy method.Additionally, the passivation layer formation composition Excellent storage stability.

【Change 3】

In logical formula (I), R¹Separately represent the alkyl of carbon number 1~8.N represents 0~3 integer.X²And X³It is only respectively On the spot represent oxygen atom or methylene.R²、R³And R⁴Separately represent the alkyl of hydrogen atom or carbon number 1~8.Here, R¹、 R²、R³、R⁴、X²And X³In either one when having multiple, the groups that the multiple for existing is represented with same symbol can be identical respectively Or it is different.

The passivation layer comprising specific organo-aluminum compound and specific alkanol salt compound is assigned on a semiconductor substrate Formation composition and form the composition layer of required shape, and it is heat-treated (burn till), it is possible thereby to will be with excellent The different passivation effect and passivation layer with fully big refractive index is formed as required shape.The method of the present invention is without evaporation Device etc., easy and productivity ratio method high.And then, it is not necessary to numerous and diverse operation such as mask process can form required shape Passivation layer.Additionally, above-mentioned passivation layer formation includes specific organo-aluminum compound and specific alkanol salt compound with composition, Therefore time dependent ground suppress gelation a problem that generation and make excellent storage stability.

In this specification, using the device of WT-2000PVN (Japanese Shi Meilebo Co., Ltd.) etc., using microwave reflection The useful life of minority carrier of the method for photoconductivity decay measurement to being formed with the semiconductor substrate of passivation layer is measured, and thus may be used To evaluate the passivation effect of semiconductor substrate.

Here, useful life τ can be according to following formula (A) like that using the bulk lifetime (bulk of semiconductor-based intralamellar part lifetime)τ_bWith the surface lifetime τ of semiconductor substrate surface_sTo represent.It is small in the surface energy level density of semiconductor substrate surface In the case of, τ_sIt is elongated, as a result make useful life τ elongated.Even if additionally, the defect such as dangling bonds of semiconductor-based intralamellar part becomes It is few, bulk lifetime τ_bAlso can be elongated, make useful life τ also elongated.I.e., it is possible to evaluate passivation layer by determining useful life τ With the bulk properties of the semiconductor substrate such as the interfacial characteristics and dangling bonds of semiconductor substrate.

1/ τ=1/ τ_b+1/τ_s (A)

In addition, useful life is more long, represent that the recombination velocity of minority carrier is slower.Additionally, by using service life Order semiconductor substrate long to constitute solar cell device, so that conversion efficiency is improved.

(specific organo-aluminum compound)

Above-mentioned passivation layer formation composition comprising the organo-aluminum compound shown at least one above-mentioned logical formula (I) (below Also referred to as " specific organo-aluminum compound ").Above-mentioned organo-aluminum compound includes the chemical combination referred to as aluminium alkoxide, aluminium chelate compound etc. Thing, also has aluminium chelate structure preferably on the basis of alkanol constructed of aluminium.Additionally, such as Nippon Seramikkusu Kyokai As Gakujitsu Ronbunshi, 97 (1989) 369-399 are described, made using heat treatment (burning till) specific organic Aluminium compound turns into aluminum oxide (Al₂O₃)。

Can be by the way that containing the organo-aluminum compound shown in logical formula (I), being formed has for passivation layer formation composition The reasons why passivation layer of excellent passivation effect, the present inventor etc. consider as follows.

Think：By to the passivation layer formation group containing specific organo-aluminum compound and specific alkanol salt compound The aluminum oxide that compound is heat-treated (burn till) and is formed easily becomes amorphous state, thus easily with semiconductor substrate Near interface forms 4 and is coordinated alumina layer, can have the larger negative fixed charge caused by 4 coordination aluminum oxide.And recognize For：The larger negative fixed charge produces electric field in the near interface of semiconductor substrate, it is possible thereby to reduce minority carrier Concentration, is as a result suppressed the carrier recombination velocity on interface, therefore can be formed with the blunt of excellent passivation effect Change layer.And then be additionally considered that：By also including specific alkanol salt compound on the basis of organo-aluminum compound, so that institute's shape Into the refractive index of passivation layer become big.

Here, state of 4 coordination alumina layers the reason for as negative fixed charge on semiconductor substrate surface can be with Confirm in the following way：Using using sweep type transmission electron microscope (STEM, Scanning Transmission Electron Microscope) ELS electron energy loss spectroscopy method (EELS, Electron Energy Loss Spectroscopy analysis), the section to semiconductor substrate investigates combination.4 coordination aluminum oxide are considered as titanium dioxide Silicon (SiO₂) center by silicon isomorphous substitution (isomorphous substitution) into the structure of aluminium, and such as zeolite and clay Be formed as negative electrical charge source at the interface of silica and aluminum oxide like that.

In addition, the state of the aluminum oxide for being formed can be by determining X-ray diffraction spectrogram (XRD, X-ray Diffraction) confirmed.For example, impalpable structure can be confirmed as because XRD does not show specific reflection graphic patterns. Additionally, the negative fixed charge that aluminum oxide has can be by CV methods (Capacitance Voltage measurement, electric capacity Voltage measurement method) evaluated.But, for the heat treatment that the aluminum oxide formed with composition is formed by passivation layer of the invention For nitride layer, the value of its surface energy level density obtained by CV methods is sometimes more than the alumina layer formed by ALD or CVD.But It is that the field effect for forming the passivation layer formed with composition by passivation layer of the invention is big and concentration of minority carrier drops It is low, make surface lifetime τ_sIt is elongated.Therefore, comparatively surface energy level density do not turn into problem.

In logical formula (I), R¹Separately represent the alkyl of carbon number 1~8, the preferably alkyl of carbon number 1~4.R¹Shown Alkyl both can be straight-chain, or branched.As R¹Shown alkyl, specifically, can enumerate methyl, second Base, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, hexyl, octyl group, 2- ethylhexyls, 3- ethylhexyls etc.. Wherein, from from the viewpoint of storage stability and passivation effect, R¹Shown alkyl is preferably the unsubstituted alkane of carbon number 1~8 The unsubstituted alkyl of base, more preferably carbon number 1~4.

In logical formula (I), n represents 0~3 integer.From from the viewpoint of storage stability, n is preferably 1~3 integer, more Preferably 1 or 3.Additionally, X²And X³Separately represent oxygen atom or methylene.From from the viewpoint of storage stability, preferably Make X²And X³In at least one party be oxygen atom.

R in logical formula (I)²、R³And R⁴Separately represent the alkyl of hydrogen atom or carbon number 1~8.R²、R³And R⁴It is shown Alkyl both can be straight-chain, or branched.R²、R³And R⁴Shown alkyl can both have substitution base, it is also possible to It is unsubstituted alkyl, preferably unsubstituted alkyl.As R²、R³And R⁴Shown alkyl, is the alkyl of carbon number 1~8, excellent Elect the alkyl of carbon number 1~4 as.As R²、R³Or R⁴Shown alkyl, is the alkyl of carbon number 1~8, preferably the alkane of carbon number 1~4 Base.Specifically, can enumerate methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, hexyl, octyl group, 2- ethylhexyls, 3- ethylhexyls etc..

Wherein, from from the viewpoint of storage stability and passivation effect, the R in logical formula (I) is preferably made²And R³Independently Ground is hydrogen atom or the unsubstituted alkyl of carbon number 1~8, the more preferably unsubstituted alkyl of hydrogen atom or carbon number 1~4.

Additionally, from from the viewpoint of storage stability and passivation effect, the R led in formula (I)⁴Preferably hydrogen atom or carbon number The unsubstituted alkyl of 1~8 unsubstituted alkyl, more preferably hydrogen atom or carbon number 1~4.

From from the viewpoint of storage stability, the organo-aluminum compound shown in logical formula (I) is preferably n for 1~3 and R⁴Point The compound of the alkyl of hydrogen atom or carbon number 1~4 independently is not.

From from the viewpoint of storage stability and passivation effect, the organo-aluminum compound shown in logical formula (I) is preferably choosing It is 0 and R from n¹Separately for carbon number 1~4 alkyl compound and integer, R that n is 1~3¹It is separately carbon The alkyl of number 1~4, X²And X³In at least one party be oxygen atom, R²And R³It is separately hydrogen atom or the alkane of carbon number 1~4 Base, R⁴It is separately at least one in the compound of hydrogen atom or the alkyl of carbon number 1~4.

Organo-aluminum compound shown in logical formula (I) is more desirably selected from n for 0 and R¹It is separately carbon number 1~4 The compound and n of unsubstituted alkyl are 1~3 integer, R¹It is separately unsubstituted alkyl, the X of carbon number 1~4² And X³In at least one party be oxygen atom, the R that combines on above-mentioned oxygen atom²Or R³For carbon number 1~4 alkyl and in X²Or X³For The R combined on above-mentioned methylene during methylene²Or R³It is hydrogen atom, R⁴It is at least one in the compound of hydrogen atom.

As the specific organo-aluminum compound (three aluminium alkoxides) that the n in logical formula (I) is 0, specifically, front three can be enumerated Aluminium alcoholates, three aluminium ethylates, aluminum isopropylate, three aluminium secondary butylates, Mono-sec-butoxyaluminium diisopropylate, three tert-butyl alcohol aluminium, three n-butanols Aluminium etc..

Additionally, as the specific organo-aluminum compound of shown in the logical formula (I), integer that n is 1~3, specifically, can Enumerate oacetic acid aluminum-diisopropoxide, methyl-acetoacetic acid aluminum-diisopropoxide, three (oacetic acid) aluminium, single acetyl third Ketone acid two (oacetic acid) aluminium, three (acetopyruvic acid) aluminium etc..

Additionally, the specific organo-aluminum compound that the n in logical formula (I) is 1~3 integer can both be used and prepared Organo-aluminum compound, it is also possible to use commercially available product.As commercially available product, for example, can enumerate Kawaken Fine Chemicals Co., the trade name of Ltd. is ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, Alumichelate M, Alumichelate D, Alumichelate A (W) etc..

Additionally, the specific organo-aluminum compound that the n in logical formula (I) is 1~3 integer can be by by above-mentioned three alkanol It is prepared by aluminium and the above-mentioned compounds mixing with 2 ad hoc structures of carbonyl.In addition it is also possible to sequestration using commercially available aluminium Compound.

When above-mentioned three aluminium alkoxide and compounds with 2 ad hoc structures of carbonyl are mixed, the alkanol of three aluminium alkoxides There is displacement with the compound of ad hoc structure and form aluminium chelate structure at least a portion of base.Can now exist as needed Solvent, in addition it is also possible to heated, the addition of catalyst etc..Replaced by making at least a portion of alkanol constructed of aluminium It is aluminium chelate structure, so that specific organo-aluminum compound is improved for the stability of hydrolysis and polymerisation, and makes blunt The storage stability for changing layer formation composition is further improved.Additionally, reactive with alkanol niobium described later, titanium alkoxide, alkanol Zirconium and silicon alkoxide are closer to easier generation is fine and close, the composite oxides that photocatalysis is small and refractive index is big.

There are 2 compounds of the ad hoc structure of carbonyl as above-mentioned, from from the viewpoint of reactivity and storage stability, It is preferably selected from least one in β-dione compounds, β-keto ester compound and diester malonate.There are 2 as above-mentioned The compound of the ad hoc structure of carbonyl, specifically, can enumerate：Acetylacetone,2,4-pentanedione, 3- methyl -2,4- pentanediones, 2,3- penta Diketone, 3- ethyl -2,4- pentanediones, 3- butyl -2,4- pentanediones, DPM dpm,dipivalomethane, β-the dione compounds such as 2,6- dimethyl -3,5- heptadione, 6- methyl -2,4- heptadione；Methyl acetoacetate, second Ethyl acetoacetic acid ethyl ester, propyl acetoacetate, isobutyl acetoacetate, butyl-acetoacetate, tert-butyl acetoacetate, acetoacetate penta The own ester of ester, isoamyl acetoacetate, acetoacetate, acetoacetate n-octyl, acetoacetate heptyl ester, acetoacetate 3- pentyl esters, 2- acetyl group cognac oil, 2- butyl ethylacetoacetates, 4,4- dimethyl -3- oxopentanoic acid methyl esters, 4- methyl - 3- oxopentanoic acid methyl esters, 2- ethyl acetoacetic esters, hexyl ethyl acetoacetate, 4- methyl -3- oxopentanoic acid first Ester, isopropyl acetoacetate, 3- oxos ethyl hexanoate, 3- oxopentanoic acid methyl esters, 3- oxopentanoics, 3- oxo caproic acids Methyl esters, 2- methyl-acetoacetic esters, 3- oxoheptanoates, 3- oxo-heptanoic acids methyl esters, 4,4- dimethyl -3- oxos The β such as methyl valerate-keto ester compound；Dimethyl malenate, diethyl malonate, dipropyl malonate, malonic acid diisopropyl Ester, dibutyl malonate, malonic acid di tert butyl carbonate, malonic acid dihexyl, malonic acid t-butyl acetate, methylmalonic acid diethyl It is ester, ethyl malonic acid diethylester, diethyl isopropyl, diethyl butylmalonate, s-Butylmalonic acid diethylester, different Diester malonates such as diethyl butylmalonate, 1- methyl butyl diethyl malonates etc..

In the case where above-mentioned specific organo-aluminum compound has aluminium chelate structure, as long as the number of aluminium chelate structure is 1~3, then there is no particular restriction.Wherein, from from the viewpoint of storage stability, the number of aluminium chelate structure is preferably 1 or 3, from From the viewpoint of solubility, the number of aluminium chelate structure is more preferably 1.The number of aluminium chelate structure for example can be by appropriate tune The blending ratio of whole above-mentioned three aluminium alkoxide and the compound that can form chelate with aluminium be controlled.In addition it is also possible to from The compound of structure needed for appropriate selection has in commercially available aluminium chelate compound.

In the organo-aluminum compound shown in logical formula (I), mixed from passivation effect and with the solvent being added as needed on From the viewpoint of property, specifically, preferably use selected from oacetic acid aluminum-diisopropoxide and aluminum isopropylate at least One kind, more preferably uses oacetic acid aluminum-diisopropoxide.

The presence of the aluminium chelate structure in above-mentioned specific organo-aluminum compound can utilize commonly used analysis side Method is confirmed.Can for example be confirmed using infrared spectroscopy spectrum, NMR spectrum, fusing point etc..

The containing ratio of the above-mentioned specific organo-aluminum compound included in above-mentioned passivation layer formation composition can basis Needs are suitably selected.From from the viewpoint of storage stability and passivation effect, the containing ratio of organo-aluminum compound is in passivation 1 mass %~70 mass %, preferably 3 mass %~60 mass %, more preferably 5 matter can be set in layer formation composition Amount %~50 mass %, more preferably 10 mass %~30 mass %.

Organo-aluminum compound both can be liquid, or solid, there is no particular restriction.It is steady from passivation effect and preservation From the viewpoint of qualitative, the stability that is preferably used under normal temperature (25 DEG C) and during using solvent to the dissolubility of solvent or point Dissipate the good specific organo-aluminum compound of property.By using such specific organo-aluminum compound, so that the shape in the presence of making Into the homogenieity of passivation layer further improve, the tendency of required passivation effect can be stably obtained.

(specific alkanol salt compound)

Passivation layer formation composition of the invention is on the basis of specific organo-aluminum compound also containing selected from alkanol At least one alkanol salt compound (being also referred to as below " specific alkanol salt compound ") in titanium, zirconium alkoxides and silicon alkoxide.Pass through Containing selected from least one compound in specific alkanol salt compound such that it is able to generate refraction together with organo-aluminum compound The big composite oxides of rate, and also can further improve passivation effect.

Compared with the passivation layer for only being formed by organo-aluminum compound, entered with composition by passivation layer formation of the invention The refractive index of the passivation layer that row is heat-treated (burning till) and is formed becomes big.For example for being formed with big blunt of refractive index on smooth surface Change for the solar cell device of layer, because the utilization ratio of light is further improved, therefore generating efficiency is improved.By passivation layer The refractive index of the passivation layer that formation composition is formed is preferably more than 1.4, more preferably more than 1.6, more preferably 1.6 ~2.5.

Used as titanium alkoxide, there is no particular restriction, can suitably select to use from commonly used titanium alkoxide.Wherein, From the viewpoint of resin contacted from the passivation layer for being difficult to make with formed etc. is decomposed, titanium alkoxide is preferably and logical formula (I) institute The organo-aluminum compound reaction shown and Composite and form the titanium alkoxide of finer and close composite oxides.As titanium alkoxide, specifically For, methyl alcohol titanium, titanium ethanolate, isopropyl titanate, normal propyl alcohol titanium, n-butyl titanium, tert-butyl alcohol titanium, titanium isobutoxide, diisopropyl can be enumerated Epoxide bis-acetylacetonate titanium, four (2- ethyl -1- hexanols) titaniums etc..Commonly known heat treatment to titanium alkoxide (burn till) and The refractive index of the titanium oxide for obtaining is larger.But, used with composition titanium oxide to be added to passivation layer formation in itself In the case of, the photocatalysis that may have by titanium oxide and cause resin contacted with passivation layer etc. in sunshine etc. Lower decomposition.On the other hand, in the case where titanium alkoxide to be applied to passivation layer formation composition, titanium alkoxide and organo-aluminium chemical combination Thing forms composite oxides together, can suppress photocatalysis, and can form the big passivation layer of refractive index.

As zirconium alkoxides, as long as with the organo-aluminum compound reaction shown in logical formula (I) and form the alkane of composite oxides Alcohol zirconium, then there is no particular restriction.As zirconium alkoxides, specifically, ethanol zirconium, zirconium iso-propoxide, zirconium-n-propylate, n-butanol can be enumerated Zirconium, zirconium tert-butoxide, acetylacetone,2,4-pentanedione zirconium, trifluoroacetylacetone (TFA) zirconium, hexafluoroacetylacetone zirconium etc..It is commonly known that heat is carried out to zirconium alkoxides The refractive index of zirconium oxide is larger obtained by treatment (burning till).But, zirconium oxide is being added to passivation layer formation combination in itself In the case of carrying out use in thing, the photocatalysis that may have by zirconium oxide and cause the resin contacted with passivation layer Deng in the lower decomposition such as sunshine.On the other hand, in the case where zirconium alkoxides to be applied to passivation layer formation composition, zirconium alkoxides Composite oxides are formed together with organo-aluminum compound, can suppress photocatalysis, and big blunt of refractive index can be formed Change layer.

Silicon alkoxide is illustrated.By to the passivation layer formation group containing the organo-aluminum compound shown in logical formula (I) The aluminum oxide that compound is heat-treated (burn till) and is formed easily becomes amorphous state, and partly generation 4 is coordinated aluminum oxide. If generation 4 is coordinated aluminum oxide, negative fixed charge is obtained.If here, including silicon alkoxide in passivation layer formation composition, leading to Overheating Treatment (burning till) generation 4 can be coordinated silica simultaneously.It is known 4 coordination silica can by isomorphous substitution make central atom from Silicon is replaced as aluminium.Therefore, when 4 coordination silica is formed in alumina layer, correspondingly can easily generate with negative fixed charge 4 coordination aluminum oxide.Although silica refractive index in itself compares aluminum oxide obtained by being heat-treated to silicon alkoxide (burn till) It is small, but aluminum oxide is coordinated as the 4 of negative fixed charge source due to easily being generated by Composite, therefore so that refraction will not be made The degree that rate declines to a great extent uses silicon alkoxide, thus obtains more excellent passivation effect.

As silicon alkoxide, as long as with the organo-aluminum compound shown in logical formula (I), titanium alkoxide, zirconium alkoxides or as needed Contained alkanol niobium reaction and form the silicon alkoxide of composite oxides, then there is no particular restriction.Wherein, silicon alkoxide is preferably following Compound shown in logical formula (II).

(R⁵O)_(4-m)SiR⁶ _m (II)

In formula (II), R⁵And R⁶Separately represent the alkyl of carbon number 1~8.N represents 0~3 integer.Here, R⁵And R⁶In either one when having multiple, the multiple R for existing⁵Or R⁶Can be identical or different respectively.

As silicon alkoxide, specifically, four methyl alcohol silicon, tetraethoxide silicon, four propyl alcohol silicon etc. can be enumerated.

In alkanol salt compound in selected from titanium alkoxide, zirconium alkoxides and silicon alkoxide, from the reaction with organo-aluminum compound From the viewpoint of property, the refractive index of the composite oxides for being generated and passivation effect, preferably use selected from titanium alkoxide and zirconium alkoxides In at least one, more preferably using selected from least one in isopropyl titanate, ethanol zirconium and zirconium iso-propoxide, further preferably make With selected from least one in isopropyl titanate and ethanol zirconium.

In passivation layer formation composition, selected from titanium alkoxide, zirconium alkoxides and silicon alkoxide in specific alkanol salt compound The total amount of containing ratio be preferably 0.5 mass %~65 mass %, more preferably 1 mass %~65 mass %, further preferably It is 2 mass %~60 mass %.

Additionally, from from the viewpoint of the refractive index and passivation effect of the composite oxides for being generated, above-mentioned specific alkoxide The content of compound is relative to the ratio between content of organo-aluminum compound shown in logical formula (I) (specific alkanol salt compound/formula (I) organo-aluminum compound shown in) be preferably 0.01~1000, more preferably 0.05~500, more preferably 0.1~ 100。

(alkanol niobium)

Passivation layer formation composition can contain at least one alkanol niobium.It is known that alkanol niobium is heat-treated (burn till) Obtained by niobium oxide refractive index it is larger, therefore be heat-treated with composition by pair also passivation layer formation comprising alkanol niobium (burning till), can obtain the bigger passivation layer of refractive index.

As alkanol niobium, as long as with the organo-aluminum compound reaction shown in logical formula (I) and form the alkane of composite oxides Alcohol niobium, then there is no particular restriction.As alkanol niobium, specifically, ethanol niobium, isopropanol niobium, normal propyl alcohol niobium, n-butanol can be enumerated Niobium, phenol niobium etc..

In the case where passivation layer formation composition contains alkanol niobium, the containing ratio of alkanol niobium is in passivation layer formation group 0.2 mass %~50 mass %, more preferably 0.5 mass %~48 mass % are preferably in the gross mass of compound, it is further excellent Elect 1 mass %~46 mass % as.

Additionally, in the case where passivation layer formation composition contains alkanol niobium, from the folding of the composite oxides for being generated Penetrate from the viewpoint of rate and passivation effect, the content of alkanol niobium relative to the organo-aluminum compound shown in logical formula (I) content it Be preferably 0.01~1000 than (organo-aluminum compound shown in alkanol niobium/logical formula (I)), more preferably 0.05~500, further Preferably 0.1~100.

And then, in the case where passivation layer formation composition contains alkanol niobium, from the folding of the composite oxides for being generated Penetrate from the viewpoint of rate and passivation effect, the total content of specific alkanol salt compound and alkanol niobium is relative to shown in logical formula (I) The ratio between content of organo-aluminum compound preferably 0.01~1000, more preferably 0.05~500, more preferably 0.1~ 100。

In passivation layer formation composition, organo-aluminum compound, specific alkanol salt compound and root shown in logical formula (I) 1 mass %~70 matter is preferably in the gross mass of passivation layer formation composition according to total containing ratio of the alkanol niobium contained by needs Amount %, more preferably 3 mass %~60 mass %, more preferably 5 mass %~50 mass %.

(resin)

Passivation layer formation composition can also be comprising at least one resin.By comprising resin, so that in semiconductor The shape stability of the composition layer for above-mentioned passivation layer formation composition being assigned on substrate and being formed further is improved, Ke Yi The region for being formed with combinations thereof nitride layer forms passivation layer according to required shape selective.

There is no particular restriction for the species of resin.Resin preferably assigns passivation layer formation composition on a semiconductor substrate When viscosity can be adjusted to be formed good pattern scope resin.As resin, specifically, can enumerate：Polyethylene Alcohol；Polyacrylamide；Polyvinyl lactam class；PVP；PEO class；Polysulfonate acid；Polyacrylamide Alkyl sulfonic acid；Cellulose；The celluloses such as the cellulose ether of carboxymethylcellulose calcium, hydroxyethyl cellulose, ethyl cellulose etc. derive Thing；Gelatin and gelatine derivative；Starch and starch derivatives；Sodium alginate and sodium alginate derivative；Xanthans and xanthans Derivative；Guar gum and guar derivative；Scleroglucan and scleroglucan derivative；Bassora gum and bassora gum derivative；Paste Essence and dextrin derivative；(methyl) acrylic resin；(methyl) acrylate (such as (methyl) alkyl acrylate tree Fat, (methyl) dimethylaminoethyl acrylate resin etc.)；Butadiene resin, styrene resin, silicone resin, these materials Copolymer etc..These resins can be used alone or be applied in combination two or more.

In these resins, from from the viewpoint of storage stability and patternability, preferably use without acid and The resinene of the functional group of alkalescence, even if being also readily able to from the viewpoint of regulation viscosity and thixotropy from when content is few, More preferably use cellulose derivative.

Additionally, the molecular weight of these resins there is no particular restriction, preferably in view of passivation layer formation composition it is required viscous Degree is suitably adjusted.From from the viewpoint of storage stability and patternability, the weight average molecular weight of above-mentioned resin is preferably 1,000~10,000,000, more preferably 3,000~5,000,000.In addition, the weight average molecular weight of resin is by using standard The standard curve of polystyrene is converted by the molecular weight distribution measured using GPC (gel permeation chromatography) and obtained.

In the case where passivation layer formation composition contains resin, containing in the passivation layer formation composition of resin Rate can be selected suitably as needed.For example in the gross mass of passivation layer formation composition, the containing ratio of resin is excellent Elect 0.1 mass %~30 mass % as.From showing to be more readily formed from the viewpoint of the thixotropy of pattern, above-mentioned containing ratio is more Preferably 1 mass %~25 mass %, more preferably 1.5 mass %~20 mass %, are still more preferably 1.5 matter Amount %~10 mass %.

In the case where passivation layer formation composition contains resin, above-mentioned in above-mentioned passivation layer formation composition has Machine aluminium compound can be selected suitably as needed with the containing ratio of above-mentioned resin.Wherein, from patternability and guarantor Deposit from the viewpoint of stability, resin preferably sets relative to the containing ratio (resin/organo-aluminum compound) of organo-aluminum compound It is 0.001~1000, more preferably 0.01~100, more preferably 0.1~1.

(higher boiling point materials)

With resin higher boiling point materials can be used together in passivation layer formation composition or use higher boiling point materials The instead material of resin.Higher boiling point materials are preferably the chemical combination that easily gasify and need not carry out ungrease treatment in heating Thing.Additionally, higher boiling point materials can particularly preferably maintain the high-viscosity higher boiling point materials of printing shape after coating is printed. As the material for meeting these conditions, for example, can enumerate the isobornyl cyclohexanol shown in logical formula (III).

【Change 4】

Isobornyl cyclohexanol shown in the logical formula (III) is " the Terusolve MTPH " being commercially obtained in that (NIPPON TERPENE CHEMICALS, INC., trade name).308 DEG C~318 DEG C of the boils up till of isobornyl cyclohexanol, And carried out using the de- of heat treatment (burning till) without as resin when the isobornyl cyclohexanol is removed from composition layer Fat treatment, is vaporized by heating and just can make it and disappear.Therefore, passivation layer formation composition is coated it is semiconductor-based In drying process after on plate, the big portion of solvent contained as needed in composition and isobornyl cyclohexanol can be removed Point, and can suppress to be heat-treated the black residue after (burning till).

In the case where passivation layer formation composition contains higher boiling point materials, the containing ratio of higher boiling point materials is in passivation layer 0.5 mass %~85 mass %, more preferably 1 mass %~80 mass % are preferably in the gross mass of formation composition, it is special You Xuanwei not 2 mass %~80 mass %.

(solvent)

Above-mentioned passivation layer formation composition can contain solvent.Contain solvent by making passivation layer formation composition, So as in the presence of easily adjustment viscosity, make imparting further improve and the tendency of passivation layer evenly can be formed.Make It is above-mentioned solvent, there is no particular restriction, can be suitably selected as needed.Wherein, it is preferably able to by the logical formula (I) of dissolving Shown organo-aluminum compound and specific alkanol salt compound and form the solvent of homogeneous solution, further preferably at least one has Machine solvent.

As solvent, specifically, can enumerate：Acetone, MEK, methyl n-propyl ketone, methyl isopropyl Ketone, methyl are just Butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl n hexyl ketone, metacetone, dipropyl ketone, DIBK, three The ketone series solvents such as methyl nonyl ketone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4- pentanediones, acetonyl acetone；Anaesthetie Ether, Methyl ethyl ether, methyl n-propyl ether, Di Iso Propyl Ether, tetrahydrofuran, methyltetrahydrofuran, dioxs, dimethyl dioxane, Ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, ethylene glycol diη-propyl ether, ethylene glycol dibutyl ethers, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl n-propyl ether, the positive fourth of diethylene glycol methyl Base ether, diethylene glycol diη-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol diola, triethylene glycol diformazan Base ether, triethylene glycol Anaesthetie Ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl n-butyl ether, the positive fourth of triethylene glycol two Base ether, triethylene glycol diola, TEG dimethyl ether, TEG Anaesthetie Ether, TEG Methylethyl Ether, TEG methyl n-butyl ether, TEG di-n-butyl ether, TEG diola, TEG two are just Butyl ether, propylene glycol dimethyl ether, propane diols Anaesthetie Ether, propane diols diη-propyl ether, propane diols dibutyl ethers, DPG Dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethylether, dipropylene glycol methyl n-butyl ether, DPG two N-propyl ether, DPG di-n-butyl ether, dipropylene glycol methyl n-hexyl ether, tripropylene glycol dimethyl, tripropylene glycol two Ethylether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol first Base n-hexyl ether, four propylene glycol dimethyl ethers, four propane diols Anaesthetie Ethers, four propylene glycol methyl ethyl ethers, four propylene glycol methyls The ether systems such as n-butyl ether, four propane diols di-n-butyl ethers, four propylene glycol methyl n-hexyl ethers, four propane diols di-n-butyl ethers are molten Agent；Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, N-amyl acetate, sec-amyl acetate, acetic acid 3- methoxybutyls, methyl amyl acetate, acetic acid 2- ethyls butyl ester, acetic acid 2- Octyl Nitrite, acetic acid 2- (2- Butoxyethoxies) ethyl ester, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, acetic acid Nonyl ester, methyl acetoacetate, ethyl acetoacetate, acetic acid diethylene ester, acetic acid TC ester, second Sour dipropylene glycol methyl ether ester, acetic acid dipropylene glycol ethyl ether ester, diacetate glycol ester, acetic acid methoxy triethylene ester, Ethyl propionate, n-butyl propionate, propionic acid isopentyl, diethy-aceto oxalate, dibutyl oxalate, methyl lactate, ethyl lactate, lactic acid N-butyl, N_amyl lactate, Ethylene glycol methyl ether propionic ester, glycol ethyl ether propionic ester, Ethylene glycol methyl ether acetic acid esters, second Glycol monoethyl ether acetate, methyl proxitol acetate, propylene glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters, The ester series solvents such as gamma-butyrolacton, gamma-valerolactone；Acetonitrile, 1-METHYLPYRROLIDONE, N- ethyl pyrrolidones, N- propyl group Pyrrolidones, N- butyl pyrrolidines ketone, N- hexyls pyrrolidones, N- cyclohexyl pyrrolidones, N,N-dimethylformamide, The aprotic polar solvents such as DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO)；Dichloromethane, chloroform, dichloroethanes, benzene, first The hydrophobic organic solvents such as benzene, dimethylbenzene, hexane, octane, ethylo benzene, 2 ethyl hexanoic acid, methyl iso-butyl ketone (MIBK), MEK；First Alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, 2- methyl butanols, It is sec-amyl alcohol, tert-pentyl alcohol, 3- methoxybutanols, n-hexyl alcohol, 2- methyl anyl alcohols, secondary hexyl alcohol, 2- ethyl butanols, secondary enanthol, just pungent Alcohol, 2-Ethylhexyl Alcohol, sec-octyl alcohol, n-nonyl alcohol, Decanol, secondary tip-nip, Exxal 12, secondary tetradecanol, secondary heptadecane Alcohol, cyclohexanol, methyl cyclohexanol, benzylalcohol, ethylene glycol, 1,2- propane diols, 1,3 butylene glycol, diethylene glycol, DPG, three The alcohol series solvents such as ethylene glycol, tripropylene glycol；Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list phenyl ether, diethyl two Alcohol monomethyl ether, TC, diethylene glycol list n-butyl ether, diethylene glycol list n-hexyl ether, the second of ethyoxyl three Glycol, TEG list n-butyl ether, propylene glycol monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, 3 third The glycol monoethers series solvent such as glycol monomethyl ether；α-terpinenes, α-terpineol, laurene, alloocimene, limonene, diamyl The terpene series solvents such as alkene, australene, nopinene, terpinol (terpineol), carvol, ocimenum, phellandrene；Water etc..These Solvent can be used alone or be applied in combination two or more.

Wherein, from from the viewpoint of the imparting to semiconductor substrate and patternability, above-mentioned solvent preferably comprises choosing At least one from terpene series solvent, ester series solvent and alcohol series solvent, more preferably comprising selected from least one in terpene series solvent.

In the case where passivation layer formation includes solvent with composition, the containing ratio of solvent considers that assigning property, pattern forms Property and storage stability are determined.For example, from from the viewpoint of the imparting of composition and patternability, the containing ratio of solvent 5 mass %~98 mass %, more preferably 10 mass %~95 mass % are preferably in passivation layer formation composition.

(other additives)

Above-mentioned passivation layer formation composition can contain acid compound or alkali compounds.In passivation layer formation group In the case that compound contains acid compound or alkali compounds, from from the viewpoint of storage stability, preferably make acid chemical combination The containing ratio of thing or alkali compounds is respectively below 1 mass %, more preferably 0.1 matter in passivation layer formation composition Amount below %.

As acid compound, Bronsted acid (bronsted acid) and lewis acid can be enumerated.Specifically, Can enumerate：The inorganic acids such as hydrochloric acid, nitric acid；Organic acids such as acetic acid etc..Additionally, as alkali compounds, cloth Lanace platform can be enumerated Moral alkali and lewis base.Specifically, can enumerate：The inorganic bases such as alkali metal hydroxide, alkaline earth metal hydroxide；Trialkyl Organic bases such as amine, pyridine etc..

(physics value)

There is no particular restriction for the viscosity of above-mentioned passivation layer formation composition, can be according to the imparting side to semiconductor substrate Method etc. is suitably selected.For example the viscosity of passivation layer formation composition can be set to 0.01Pas~10000Pas.Its In, from from the viewpoint of patternability, the viscosity of passivation layer formation composition is preferably 0.1Pas~1000Pas. In addition, above-mentioned viscosity uses rotary shear viscosity meter at 25 DEG C with shear rate 1.0s^-1It is measured.

Additionally, the shear viscosity of passivation layer formation composition there is no particular restriction, preferably make passivation layer formation combine Thing has thixotropy.Especially in the case where passivation layer formation includes resin with composition, from from the viewpoint of patternability, Shear rate 1.0s^-1When shear viscosity η₁Divided by shear rate 10s^-1When shear viscosity η₂And thixotropic ratio (the η for calculating₁/η₂) Preferably 1.05~100, more preferably 1.1~50.In addition, shear viscosity is using being provided with cone-plate (1 ° of diameter 50mm, cone angle) Rotary shear viscosity meter be measured at 25 DEG C of temperature.

On the other hand, in the case where passivation layer formation contains higher boiling point materials with composition come instead of resin, from pattern From the viewpoint of formative, shear rate 1.0s^{- 1}When shear viscosity η₁Divided by shear rate 1000s^{- 1}When shear viscosity η₃ And thixotropic ratio (the η for calculating₁/η₃) it is preferably 1.05~100, more preferably 1.1~50.

(manufacture method of passivation layer formation composition)

For the manufacture method of above-mentioned passivation layer formation composition, there is no particular restriction.For example, can be beneficial to generally making Mixed method by the organo-aluminum compound shown in logical formula (I), specific alkanol salt compound and resin contained as needed, Solvent etc. mixes, so as to manufacture above-mentioned passivation layer formation composition.Further, it is also possible to by after resin is dissolved in into solvent It is mixed with the organo-aluminum compound shown in logical formula (I) and specific alkanol salt compound to manufacture above-mentioned passivation layer formation group Compound.

And then, logical formula (I) institute can also be prepared by the way that aluminium alkoxide, the compound that can form chelate with aluminium are mixed The organo-aluminum compound for showing.At this point it is possible to use solvent as needed, it is also possible to heated.Can also by by this Organo-aluminum compound and specific alkanol salt compound shown in the logical formula (I) of sample preparation mix with resin or the resiniferous solution of bag To manufacture passivation layer formation composition.

In addition, the content of composition contained in above-mentioned passivation layer formation composition and each composition can using differential heat- Thermogravimetric amount determines spectrum analysis, the efficient liquid such as heat analysis, nuclear magnetic resonance (NMR), infra-red sepectrometries (IR) such as (TG/DTA) simultaneously Chromatography such as phase chromatogram (HPLC), gel permeation chromatography (GPC) etc. are confirmed.

Semiconductor substrate ＞s of the ＜ with passivation layer

Semiconductor substrate with passivation layer of the invention, it has semiconductor substrate and is arranged on above-mentioned semiconductor substrate Whole face or a part passivation layer, the passivation layer is that the heat treatment thing of passivation layer formation composition of the invention (burns till Thing).The above-mentioned semiconductor substrate with passivation layer is by the heat treatment nitride layer (burned material with above-mentioned passivation layer formation composition Layer) it is passivation layer and shows excellent passivation effect.

There is no particular restriction for semiconductor substrate, can be carried out suitably from commonly used semiconductor substrate according to purpose Selection.Used as semiconductor substrate, can be set forth in the middle doping such as silicon, germanium (diffusion) has the semiconductor-based of n-type impurity or p-type impurity Plate.Wherein, preferably silicon substrate.Additionally, semiconductor substrate both can be p-type semiconductor substrate, or n-type semiconductor base Plate.Wherein, from from the viewpoint of passivation effect, the face for preferably forming passivation layer is the semiconductor substrate of p-type layer.It is above-mentioned partly to lead P-type layer on structure base board can both be derived from the p-type layer of p-type semiconductor substrate, or with p-diffusion layer or p⁺Type expands Dissipate the p-type layer that the form of layer is formed on n-type semiconductor substrate or p-type semiconductor substrate.

Additionally, the thickness of above-mentioned semiconductor substrate there is no particular restriction, can suitably be selected according to purpose.For example, The thickness of semiconductor substrate can be set to 50 μm~1000 μm, preferably 75 μm~750 μm.

There is no particular restriction for the average thickness of the passivation layer being formed on above-mentioned semiconductor substrate, can be carried out according to purpose Appropriate selection.For example, the average thickness of passivation layer is preferably 5nm~50 μm, more preferably 10nm~30 μm, more preferably 15nm~20 μm.The average thickness of passivation layer can be using interfering formula film thickness gauge etc. to determine.

The above-mentioned semiconductor substrate with passivation layer can apply to solar cell device, light-emitting diode etc..Example Such as, by being applied to solar cell device, it is hereby achieved that the excellent solar cell device of conversion efficiency.Will be above-mentioned In the case that semiconductor substrate with passivation layer is applied to solar cell device, passivation layer is preferably provided at solar cell unit The light surface side of part.

The manufacture method ＞ of semiconductor substrates of the ＜ with passivation layer

The manufacture method of the semiconductor substrate with passivation layer of the invention, it includes：To the whole face on semiconductor substrate or A part assigns passivation layer formation composition of the invention and forms the operation of composition layer；Carried out with to combinations thereof nitride layer Heat treatment (burning till) and form the operation of passivation layer.Above-mentioned manufacture method can also further contain other operations as needed.

By using above-mentioned passivation layer formation composition, required shape can be formed and with excellent in easy method The passivation layer of passivation effect and larger refractive index.

The manufacture method of the above-mentioned semiconductor substrate with passivation layer was preferably gone back before the operation of combinations thereof nitride layer is formed With the operation for assigning aqueous alkali on a semiconductor substrate.That is, preferably it is imparted to composition by above-mentioned passivation layer formation With the surface of aqueous alkali washing semi-conductor substrate before on semiconductor substrate.Washed by with aqueous alkali, can be removed Remove to be present in organic matter, particulate of semiconductor substrate surface etc., and passivation effect is further improved.As molten using buck The washing methods of liquid, can illustrate commonly known RCA washings etc..For example, semiconductor substrate impregnated in into ammoniacal liquor-peroxidating In the mixed solution of hydrogen water, and processed at 60 DEG C~80 DEG C, it is possible thereby to remove organic matter and particulate and washed. Wash time is preferably 10 seconds~10 minutes, more preferably 30 seconds~5 minutes.

In RCA washings, first, semiconductor substrate is put into the diluted hydrofluoric acid aqueous solution (HF), makes the relatively thin of surface Si oxide-films are dissolved, and the multiple foreign matters that will be attached to thereon are also removed simultaneously.And then, as described above using ammoniacal liquor (NH₄OH)-hydrogen peroxide (H₂O₂) mixed solution remove organic matter and particulate, then, using hydrochloric acid (HC1) and hydrogen peroxide (H₂O₂) remove metal class.Then, last washing is completed using ultra-pure water.

The method for assigning above-mentioned passivation layer formation composition on a semiconductor substrate and forming composition layer has no especially Limitation.For example, can enumerate that above-mentioned passivation layer formation composition is assigned on a semiconductor substrate using known coating method etc. Method.Specifically, infusion process, print process, spin-coating method, spread coating, spray-on process, scraper plate method, rolling method, ink-jet method can be enumerated Deng.Wherein, from from the viewpoint of patternability, preferably various print processes, ink-jet method etc..

Above-mentioned passivation layer formation can suitably be selected with the imparting amount of composition according to purpose.For example, can be according to Make formed passivation layer thickness turn into it is aftermentioned needed for the mode of thickness suitably adjust the imparting of passivation layer formation composition Amount.

It is heat-treated (burn till) and is formed from above-mentioned to forms the composition layer formed with composition by passivation layer The heat treatment nitride layer (burning till nitride layer) of composition layer, such that it is able to form passivation layer on a semiconductor substrate.

Heat treatment (burning till) condition on composition layer, as long as can be by shown in logical formula (I) contained in composition layer Organo-aluminum compound and specific alkanol salt compound be converted into as its be heat-treated thing (burned material) aluminum oxide (Al₂O₃) and Composite oxides, then be not particularly limited.Wherein, it is preferably able to be formed comprising without specific crystalline texture and amorphous Al₂O₃Layer heat treatment (burning till) condition.By making passivation layer by the Al comprising amorphous₂O₃Layer constitute, can more have Effect ground makes passivation layer negatively charged, and can obtain more excellent passivation effect.Specifically, heat treatment (burning till) temperature is excellent Elect 400 DEG C~900 DEG C, more preferably 450 DEG C~800 DEG C as.Additionally, heat treatment (burning till) time (can burn according to heat treatment Into) temperature etc. suitably selected.Can for example be set to 0.1 hour~10 hours, preferably 0.2 hour~5 hours.

There is no particular restriction for the thickness of the passivation layer manufactured using the manufacture method of the above-mentioned semiconductor substrate with passivation layer, Can suitably be selected according to purpose.The average thickness of such as passivation layer is preferably 5nm~50 μm, more preferably 10nm~30 μm, more preferably 15nm~20 μm.

In addition, the average thickness of the passivation layer for being formed is by using contact pin type difference in height-surface-profile measuring instrument (example Such as Ambios companies), interference formula film thickness gauge (such as FILMETRICS companies) and conventionally determine 3 points of thickness, Its arithmetic mean of instantaneous value is calculated again.

The manufacture method of the above-mentioned semiconductor substrate with passivation layer can assign passivation layer formation composition after and Also have to forming the composition formed with composition by passivation layer before the operation that passivation layer is formed using heat treatment (burning till) The withering operation of layer.By with to the withering operation of composition layer, being formed with evenly Passivation effect passivation layer.

As long as can be included in passivation layer formation composition to the withering operation of composition layer Solvent at least a portion remove, then there is no particular restriction.Dried process can for example be set to be carried out at 30 DEG C~250 DEG C The heating of 1 minute~60 minutes, preferably carries out the heating of 3 minutes~40 minutes at 40 DEG C~220 DEG C.This Outward, dried process can both be carried out at ambient pressure, it is also possible to be carried out under reduced pressure.

In the case where passivation layer formation includes resin with composition, the manufacturer of the above-mentioned semiconductor substrate with passivation layer Method can also have before the operation of passivation layer is formed after assigning passivation layer formation composition and using heat treatment (burning till) The operation of ungrease treatment is carried out to forming the composition layer formed with composition by passivation layer.Due to being carried out to composition layer The operation of ungrease treatment, therefore the passivation layer with semiconductor substrate passivation effect evenly can be formed.

As long as the operation of ungrease treatment is carried out to composition layer can be included in passivation layer formation composition Resin at least a portion remove, then there is no particular restriction.Ungrease treatment can for example be set to enter at 250 DEG C~400 DEG C The row heating of 3 minutes~120 minutes, is preferably carried out at the heating of 10 minutes~60 minutes at 300 DEG C~450 DEG C Reason.Additionally, ungrease treatment is preferably carried out in the presence of oxygen, more preferably carry out in an atmosphere.

＜ solar cell devices ＞

Solar cell device of the invention, it has：P-type layer and n-layer are carried out into the semiconductor-based of pn engagements Plate；The whole face being arranged on above-mentioned semiconductor substrate or the passivation layer of a part, the passivation layer are passivation layer shape of the invention Into the heat treatment thing (burned material) with composition；Be configured at above-mentioned semiconductor substrate selected from above-mentioned p-type layer and above-mentioned n-layer In the layer of more than 1 on electrode.Above-mentioned solar cell device can further have other inscapes as needed.

Above-mentioned solar cell device forms the passivation layer formed with composition by having by passivation layer of the invention, from And make conversion efficiency excellent.

Used as the semiconductor substrate for assigning passivation layer formation composition, there is no particular restriction, can be according to purpose from logical Suitably selected in the semiconductor substrate for often being used.As semiconductor substrate, it is possible to use in the semiconductor with passivation layer The semiconductor substrate illustrated in substrate, the semiconductor substrate that can be preferably used is similarly.The semiconductor of above-mentioned passivation layer is set The face of substrate both can be p-type layer, or n-layer.Wherein, from from the viewpoint of conversion efficiency, preferably p-type layer.On State the p-type layer on semiconductor substrate can both be derived from p-type semiconductor substrate p-type layer, or with p-diffusion layer or p⁺The form of type diffusion layer is formed at the p-type layer on n-type semiconductor substrate or p-type semiconductor substrate.Additionally, setting above-mentioned passivation The face of the semiconductor substrate of layer is preferably the smooth surface in solar cell device.

There is no particular restriction for the thickness of above-mentioned semiconductor substrate, can suitably be selected according to purpose.Can for example set It is 50 μm~1000 μm, preferably 75 μm~750 μm.

Additionally, the thickness of the passivation layer being formed on above-mentioned semiconductor substrate there is no particular restriction, can be entered according to purpose The appropriate selection of row.The average thickness of such as passivation layer is preferably 5nm~50 μm, more preferably 10nm~30 μm, further preferably It is 15nm~20 μm.

Shape, size for above-mentioned solar cell device etc. are simultaneously unrestricted.For example, it is preferable to for the length of side be 125mm~ The square of 156mm.

The manufacture method ＞ of ＜ solar cell devices

The manufacture method of solar cell device of the invention, it includes：To with by p-type layer and n-layer engagement form Pn-junction and the layer of more than 1 in selected from p-type layer and n-layer on have electrode it is semiconductor substrate, with above-mentioned electricity At least a portion in the face of pole, assigns passivation layer formation composition of the invention and forms the operation of composition layer；With to upper State the operation that composition layer is heat-treated (burn till) and forms passivation layer.The manufacture method of above-mentioned solar cell device can be with Further there are other operations as needed.

By using above-mentioned passivation layer formation composition, can possess with excellent passivation effect with easy method manufacture Fruit and the big passivation layer of refractive index and the excellent solar cell device of conversion efficiency.And then, electrode can be formed with Passivation layer is formed according to required shape on semiconductor substrate, makes the productivity ratio of solar cell device excellent.

Be configured with the layer of at least one party in p-type layer and n-layer electrode, the semiconductor substrate with pn-junction can be with Manufactured using commonly used method.For example, the desired zone in semiconductor substrate assigns the electrodes such as silver paste agent, Aluminum Paste Formation paste, and be heat-treated as needed (burn till), it is possible thereby to manufacture the semiconductor substrate.

The face for setting the semiconductor substrate of above-mentioned passivation layer both can be p-type layer, or n-layer.Wherein, from conversion From the viewpoint of efficiency, preferably p-type layer.

The details of the method for forming passivation layer using above-mentioned passivation layer formation composition with described The manufacture method of the semiconductor substrate with passivation layer is identical, and preferred mode is also identical.

There is no particular restriction for the thickness of the passivation layer being formed on above-mentioned semiconductor substrate, can be carried out suitably according to purpose Selection.The average thickness of such as passivation layer is preferably 5nm~50 μm, more preferably 10nm~30 μm, more preferably 15nm ~20 μm.

Embodiments of the present invention are illustrated referring to the drawings.

(d) of (a) of Fig. 1~Fig. 1 be with section view diagram form schematically show present embodiment with passivation layer too The process chart of of the manufacture method of positive energy cell device.But, the process chart is to the present invention without any limitation.

As shown in (a) of Fig. 1, n is formed in the near surface of p-type semiconductor substrate 1⁺Type diffusion layer 2, and in most surface Form antireflection film 3.As antireflection film 3, silicon nitride film, oxidation titanium film etc. can be enumerated.In antireflection film 3 and p-type semiconductor Can further there is the surface protection film (not shown) of silica etc. between substrate 1.Further, since passivation layer of the invention Refractive index is larger, therefore the passivation layer (not shown) is preferably formed between antireflection film 3 and p-type semiconductor substrate 1.Although Do not make diagram in (d) of (a) of Fig. 1~Fig. 1, but below by using Fig. 3 to there is passivation layer too in light surface side The manufacture method of positive energy cell device is described.

Then, as shown in (b) of Fig. 1, aluminium electrode paste is coated with a part of region at the back side of p-type semiconductor substrate 1 After etc. the material for forming backplate 5, it is heat-treated (burn till) and is formed backplate 5, and aluminium atom is diffused into p-type P is formed in semiconductor substrate 1⁺Type diffusion layer 4.

Then, as shown in (c) of Fig. 1, after the light surface side coating electrode formation paste of p-type semiconductor substrate 1, enter Row is heat-treated (burning till) and forms smooth surface electrode 7.By using containing the glass dust with burn through (fire through) property The material at end as electrode formation paste, can as shown in (c) of Fig. 1 insertion antireflection film 3, and in n⁺Type diffusion layer Smooth surface electrode 7 is formed on 2 and obtain Ohmic contact.

In addition, in (d) of (a)~Fig. 1 of Fig. 1, entering (c) of (b) of Fig. 1 and Fig. 1 as each independent operation Diagram is gone, but it is also possible to which the operation of (c) of (b) of Fig. 1 and Fig. 1 is merged into 1 operation.Specifically, can be above-mentioned A part of region in (b) of Fig. 1 overleaf is coated with after the material of the formation backplate 5 such as aluminium electrode paste and carries out for shape Into before the heat treatment (burning till) of backplate 5, electrode formation paste is coated on light surface side, is then carried out in the stage Heat treatment (burning till).In the case of the method, form the electrode of the back side and smooth surface to simplify operation using 1 heat treatment.

Then, as shown in (d) of Fig. 1, assigned in the back side p-type layer in addition to the region of backplate 5 is formed with blunt Change layer formation composition and form composition layer.Imparting can be carried out for example, by methods such as silk-screen printings.To being formed at p Composition layer on type layer is heat-treated (burn till) and is formed passivation layer 6.By being formed by above-mentioned passivation in overleaf p-type layer The passivation layer 6 that layer formation is formed with composition, can manufacture the excellent solar cell device of generating efficiency.

In the solar cell unit for utilizing the manufacture method of manufacturing process shown in (d) that includes (a)~Fig. 1 of Fig. 1 to manufacture In part, the backplate formed by aluminium etc. can be made point-contact junction structure, and the warpage of substrate can be reduced etc..And then, By using above-mentioned passivation layer formation composition, can be only in specific position (specifically except the area for being formed with electrode In p-type layer beyond domain) passivation layer is formed with excellent productivity ratio.

Only form the method for passivation layer in the back portion of semiconductor substrate 1 additionally, being shown in (d) of Fig. 1, but also may be used Passivation layer formation is also assigned with the side in addition to rear side in semiconductor substrate 1 to be heat-treated with composition and to it (burning till), so as to also form passivation layer 6 (not shown) in the side (edge) of semiconductor substrate 1.Thereby, it is possible to manufacture the effect that generates electricity The more excellent solar cell device of rate.

Further, it is also possible to overleaf part does not form passivation layer and is only coated with passivation layer formation group of the invention in side Compound is simultaneously heat-treated (burn till) to it, so as to form passivation layer.Passivation layer formation composition of the invention is for picture During position more than crystal defect as side, its effect is especially big.

The mode that passivation layer is formed after electrode is formed is illustrated in (d) of (a) of Fig. 1~Fig. 1, but it is also possible to After passivation layer is formed the electrode of aluminium etc. is formed further with evaporation etc. in required region.

(e) of (a) of Fig. 2~Fig. 2 is the tool that a present embodiment of the invention is schematically shown with section view diagram form There is the process chart of another of the manufacture method of the solar cell device of passivation layer.Specifically, (a) of Fig. 2~Fig. 2 E () is to include the process chart of following operation with the explanation of section view diagram form：Using aluminium electrode paste or can be using at thermal diffusion Reason forms p⁺The p-diffusion layer formation of type diffusion layer forms p with composition⁺After type diffusion layer, remove at the heat of aluminium electrode paste The heat treatment thing of reason thing or p-diffusion layer formation composition.Here, as p-diffusion layer formation composition, such as can arrange Lift the composition containing material containing recipient element and glass ingredient.

As shown in (a) of Fig. 2, n is formed in the near surface of p-type semiconductor substrate 1⁺Type diffusion layer 2, and formed on surface Antireflection film 3.As antireflection film 3, silicon nitride film, oxidation titanium film etc. can be enumerated.

Then, as shown in (b) of Fig. 2, after a part of region imparting p-type diffusion layer formation composition overleaf, enter Row is heat-treated and forms p⁺Type diffusion layer 4.In p⁺The heat treatment thing 8 of p-diffusion layer formation composition is formed on type diffusion layer 4.

Herein, it is possible to use aluminium electrode paste is instead of p-diffusion layer formation composition.In the feelings using aluminium electrode paste Under condition, in p⁺Aluminium electrode 8 is formed on type diffusion layer 4.

Then, as shown in (c) of Fig. 2, removed using methods such as etchings and be formed at p⁺P-diffusion layer on type diffusion layer 4 The heat treatment thing 8 or aluminium electrode 8 of formation composition.

Then, as shown in (d) of Fig. 2, in the smooth surface (surface) and a part of regional choice at the back side of semiconductor substrate 1 Property ground coating electrode formation paste after, be heat-treated and formed smooth surface electrode 7 in smooth surface (surface), and overleaf Form backplate 5.By using the material containing the glass powder with burn through as the electrode for coating light surface side Formation paste, can as shown in (d) of Fig. 2 insertion antireflection film 3, and in n⁺Smooth surface electricity is formed on type diffusion layer 2 Pole 7 and obtain Ohmic contact.

Further, since having formed p in the region for forming backplate⁺Type diffusion layer 4, thus be accordingly used in form backplate 5 electrode formation paste is not limited to aluminium electrode paste, it is also possible to can form more low resistance using silver electrode paste etc. Electrode electrode paste.Thus, it is also possible to further improve generating efficiency.

Then, as shown in (e) of Fig. 2, assigned in the back side p-type layer in addition to the region of backplate 5 is formed with blunt Change layer formation composition and form composition layer.Imparting can be carried out for example, by methods such as silk-screen printings.To being formed at p Composition layer on type layer is heat-treated (burn till) and is formed passivation layer 6.By being formed by the present invention in p-type layer overleaf The passivation layer 6 that is formed with composition of passivation layer formation, the excellent solar cell device of generating efficiency can be manufactured.

Additionally, showing the method for only forming passivation layer in the back portion of semiconductor substrate 1 in (e) of Fig. 2, but it is also possible to Also assign passivation layer formation and be heat-treated with material and to it in the side in addition to rear side of p-type semiconductor substrate 1 and (burn Into), so as to also form passivation layer (not shown) in the side (edge) of p-type semiconductor substrate 1.Thereby, it is possible to manufacture the effect that generates electricity The more excellent solar cell device of rate.

Further, it is also possible to overleaf part does not form passivation layer and is only assigned in the side of semiconductor substrate of the invention blunt Change layer formation to be heat-treated (burn till) with composition and to it, so as to form passivation layer.Passivation layer formation group of the invention During position of the compound more than the crystal defect as image side surface, its effect is especially big.

The mode that passivation layer is formed after electrode is formed is illustrated in (e) of (a) of Fig. 2~Fig. 2, but it is also possible to After passivation layer is formed the electrode of aluminium etc. is formed further with evaporation etc. in required region.

N is formed with smooth surface to use in the above-described embodiment⁺The situation of the p-type semiconductor substrate of type diffusion layer is entered Go explanation, but using being formed with p in smooth surface⁺In the case of the n-type semiconductor substrate of type diffusion layer, it is also possible to similarly make Make solar cell device.It should be noted that now, overleaf side forms n⁺Type diffusion layer.

And then, passivation layer formation composition can be used for being formed as shown in Figure 3 that only overleaf side is configured with electricity The light surface side of the back electrode type solar cell device of pole or the passivation layer 6 of rear side.

As shown in the schematic cross sectional views of Fig. 3, the near surface in the light surface side of p-type semiconductor substrate 1 forms n⁺Type Diffusion layer 2, and form passivation layer 6 and antireflection film 3 on its surface.As antireflection film 3, it is known that silicon nitride film, oxidation titanium film Deng.Additionally, passivation layer 6 is heat-treated (burn till) come shape by assigning passivation layer formation of the invention with composition and to it Into.Because passivation layer of the invention shows good refractive index, it is taken as that smooth surface can be arranged on by by the passivation layer Improve generating efficiency is carried out in side.

In the p of the rear side of p-type semiconductor substrate 1⁺Type diffusion layer 4 and n⁺Backplate 5 is respectively provided with type diffusion layer 2, And then the region for not forming electrode overleaf sets passivation layer 6.

p⁺Type diffusion layer 4 can be coated with p-diffusion layer formation composition or aluminium by desired zone as described above It is heat-treated after electrode paste agent formed.Additionally, n⁺Type diffusion layer 2 can be coated with energy for example, by required region Enough n is formed using heat diffusion treatment⁺The n-type diffusion layer formation of type diffusion layer is formed with being heat-treated to it after composition.

Here, as n-type diffusion layer formation composition, such as can enumerate and contain material containing donor element and glass ingredient Composition.

It is separately positioned on p⁺Type diffusion layer 4 and n⁺Backplate 5 on type diffusion layer 2 can be by using silver electrode paste Formed with paste etc. usually used electrode formation.

Additionally, being arranged on p⁺Backplate 5 on type diffusion layer 4 can also be to use aluminium electrode paste and p⁺Type diffusion layer 4 The aluminium electrode for being formed together.

The passivation layer 6 for setting overleaf can assign passivation layer formation group by the region for being not provided with backplate 5 Compound and be heat-treated (burn till) to it is formed.

Additionally, passivation layer 6 can not only be formed in the back side of semiconductor substrate 1, and it is additionally formed in side and (does not scheme Show).

In the back electrode type solar cell device shown in Fig. 3, due to not having electrode, therefore hair in light surface side Electrical efficiency is excellent.And then, because the region for not forming electrode overleaf forms passivation layer, therefore make conversion efficiency more excellent.

It is illustrated above to use p-type semiconductor substrate as the example of semiconductor substrate, but using n-type semiconductor substrate When the excellent solar cell device of conversion efficiency can also be manufactured according to above-mentioned.Shape for solar cell device, Size is simultaneously unrestricted, and the preferably common length of side is the square of 125mm~156mm.

＜ solar cells ＞

Solar cell has solar cell device of the invention and is configured at the electrode of above-mentioned solar cell device On wiring material.Solar cell can also connect multiple solar cell units by wiring materials such as lug lines as needed Part is simultaneously sealed using encapsulant.

Used as above-mentioned wiring material and encapsulant, there is no particular restriction, can be from the usually used material of the art Suitably selected in material.

Size for above-mentioned solar cell is simultaneously unrestricted.Solar cell is preferably sized to 0.5m²~3m²。

Embodiment

Hereinafter, the present invention is further illustrated using embodiment, but the present invention is not limited to the examples. In addition, as long as no special declaration, then " % " is quality criteria.

The ＞ of ＜ embodiments 1

(passivation layer is formed with the preparation of composition 1)

Ethyl cellulose (is evolved into Co., Ltd., trade name day：ETHOCEL200cps) 5.00g and terpineol (NIPPON TERPENE CHEMICALS, INC.) 95.02g mixes, and is stirred 1 hour at 150 DEG C, is prepared into ethyl cellulose Solution.

Then, by oacetic acid aluminum-diisopropoxide (Kawaken Fine Chemicals Co., Ltd.s, trade name： ALCH) 15.1g, ethanol niobium (Wako Pure Chemical Industries, Ltd.) 5.1g, titanium tetraisopropylate (Wako Pure Chemical Industries, Ltd.) 5.0g, above-mentioned ethyl cellulose solution 35.2g and terpineol (NIPPON TERPENE CHEMICALS, INC.) 30.2g mix, It is prepared into passivation layer formation composition 1.

(formation of passivation layer)

The use of surface is monocrystalline type p-type silicon substrate (SUMCO Co. Ltd. systems, 50mm square, the thickness of mirror shape：625 μm) as semiconductor substrate.Use RCA cleaning solutions (Kanto Kagaku K. K., trade name：Frontier Cleaner- A01 thus silicon substrate dipping washing 5 minutes pre-treatment) has been carried out at 70 DEG C.

Then, using silk screen print method, according to the mode for making dried thickness reach 5 μm in the silicon substrate by preceding treatment The passivation layer formation composition 1 of above-mentioned acquisition is assigned on the whole face of plate, 5 minutes dried process are carried out at 150 DEG C.Then, After carrying out being heat-treated (burning till) in 10 minutes at 700 DEG C, cooling is placed at room temperature, be thus fabricated to evaluation substrate.

＜ evaluates ＞

The evaluation that passivation layer formation obtained above is fabricated to composition and using said composition is carried out with substrate It is following to evaluate, and evaluation result is shown in table 1.

(evaluation of thixotropic ratio)

In rotary shear viscosity meter (AntonPaar companies, trade name：Cone-plate (diameter 50mm, cone are installed on MCR301) 1 ° of angle), and in 25 DEG C of temperature, shear rate 1.0s^-1And 10s^-1Under conditions of respectively to upper (within 12 hours) immediately after preparation The shear viscosity for stating obtained passivation layer formation composition 1 is determined.

It is 1.0s in shear rate^-1Under conditions of shear viscosity (η₁) it is 44.0Pas, it is 10s in shear rate^-1's Under the conditions of shear viscosity (η₂) it is 35.0Pas.Shear viscosity is 1.0s^-1And 10s^-1When thixotropic ratio (η₁/η₂) it is 1.3.

(evaluation of storage stability)

After being preserved 30 days (within 12 hours) and at 25 DEG C immediately after preparation, respectively to passivation layer shape obtained above It is determined into the shear viscosity of composition 1.Cone-plate (diameter is installed on MCR301 (trade name, AntonPaar companies) 1 ° of 50mm, cone angle), and in 25 DEG C of temperature, shear rate 1.0s^-1Under carried out the measure of shear viscosity.

Shear viscosity (the η at 25 DEG C immediately after preparation₀) it is 44.0Pas, at 25 DEG C after being preserved 30 days at 25 DEG C Shear viscosity (η₃₀) it is 44.6Pas.

The rate of change of the shear viscosity after being preserved 30 days at 25 DEG C is calculated according to following formula (B), and according to following evaluations Benchmark is evaluated storage stability.

Rate of change (%)=(η of shear viscosity₃₀- η₀)/(η₀)×100 (B)

[metewand]

A：The rate of change of shear viscosity is less than 10%.

B：The rate of change of shear viscosity is 10% less than 30%.

C：The rate of change of shear viscosity is more than 30%.

If being evaluated as A or B, as being good for passivation layer formation composition.

(measure of useful life)

Service life determines device (Japanese Shi Meilebo Co., Ltd., trade name：WT-2000PVN), in room temperature (25 DEG C) under the useful life (μ s) of the evaluation substrate of above-mentioned acquisition is determined using Photoconductivity decay by microwave reflectance damped method. The useful life in the region for imparting semiconductor substrate passivation layer formation composition of the evaluation substrate for being obtained is 300 μ s。

(thickness of passivation layer and the measure of refractive index)

Using interference formula film thickness gauge (FILMETRICS Co., Ltd., F20 film thickness measuring system) to evaluation obtained above It is determined with the average thickness and refractive index of the passivation layer on substrate.The thickness of passivation layer is 220nm, and refractive index is 1.71。

The ＞ of ＜ embodiments 2

(passivation layer is formed with the preparation of composition 2)

By oacetic acid aluminum-diisopropoxide 14.9g, titanium tetraisopropylate 9.8g, above-mentioned ethyl cellulose solution 35.1g And terpineol 29.7g mixing, it is prepared into passivation layer formation composition 2.

In addition to using passivation layer formation with composition 2, evaluated similarly to Example 1, shown the result in In table 1.

The ＞ of ＜ embodiments 3

(passivation layer is formed with the preparation of composition 3)

By oacetic acid aluminum-diisopropoxide 15.0g, ethanol zirconium (Wako Pure Chemical Industries, Ltd.) 10.2g, above-mentioned Ethyl cellulose solution 35.1g and terpineol 30.4g mixes, and is prepared into passivation layer formation composition 3.

In addition to using passivation layer formation with composition 3, evaluated similarly to Example 1, shown the result in In table 1.

The ＞ of ＜ embodiments 4

(passivation layer is formed with the preparation of composition 4)

By oacetic acid aluminum-diisopropoxide 15.2g, ethanol niobium 10.0g, titanium ethanolate 5.1g, tetraethyl orthosilicate (and Wako Pure Chemical Industries Co., Ltd.) 4.8g, above-mentioned ethyl cellulose solution 34.7g and terpineol 30.3g mixing, be prepared into passivation layer Formed and use composition 4.

In addition to using passivation layer formation with composition 4, evaluated similarly to Example 1, shown the result in In table 1.

The ＞ of ＜ embodiments 5

(passivation layer is formed with the preparation of composition 5)

Oacetic acid aluminum-diisopropoxide 14.9g, titanium ethanolate 15.2g, tetraethyl orthosilicate 5.2g, above-mentioned ethyl is fine Dimension element solution 34.8g and terpineol 30.6g mixing, is prepared into passivation layer formation composition 5.

In addition to using passivation layer formation with composition 5, evaluated similarly to Example 1, shown the result in In table 1.

The ＞ of ＜ embodiments 6

(passivation layer is formed with the preparation of composition 6)

Oacetic acid aluminum-diisopropoxide 15.0g, ethanol zirconium 15.1g, tetraethyl orthosilicate 5.1g, above-mentioned ethyl is fine Dimension element solution 35.3g and terpineol 29.6g mixing, is prepared into passivation layer formation composition 6.

In addition to using passivation layer formation with composition 6, evaluated similarly to Example 1, shown the result in In table 1.

The ＞ of ＜ embodiments 7

(passivation layer is formed with the preparation of composition 7)

By oacetic acid aluminum-diisopropoxide 15.1g, ethanol niobium 5.0g, isopropyl titanate 5.0g, isobornyl cyclohexanol (NIPPON TERPENE CHEMICALS, INC., trade name：Terusolve MTPH) 35.2g and terpineol 14.9g mixing, It is prepared into passivation layer formation composition 7.

In addition to using passivation layer formation with composition 7, evaluated similarly to Example 1, shown the result in In table 1.In addition, thixotropic ratio is with shear rate as 1.0s^{- 1}When shear viscosity (η₁) with shear rate be 1000s^{- 1}When shearing Viscosity (η₃) the ratio between (η₁/η₃) form calculate.

The ＞ of ＜ embodiments 8

(passivation layer is formed with the preparation of composition 8)

By oacetic acid aluminum-diisopropoxide 15.2g, isopropyl titanate 10.2g, isobornyl cyclohexanol 34.8g and terpin Alcohol 15.2g mixes, and is prepared into passivation layer formation composition 8.

In addition to using passivation layer formation with composition 8, evaluated together with embodiment 1, shown the result in table 1 In.In addition, thixotropic ratio is with shear rate as 1.0s^{- 1}When shear viscosity (η₁) with shear rate be 1000s^{- 1}When shearing glue Degree (η₃) the ratio between (η₁/η₃) form calculate.

The ＞ of ＜ embodiments 9

(passivation layer is formed with the preparation of composition 9)

By oacetic acid aluminum-diisopropoxide 14.8g, ethanol zirconium 9.8g, isobornyl cyclohexanol 35.5g and terpineol 15.2g mixes, and is prepared into passivation layer formation composition 9.

In addition to using passivation layer formation with composition 9, evaluated similarly to Example 1, shown the result in In table 1.In addition, thixotropic ratio is with shear rate as 1.0s^{- 1}When shear viscosity (η₁) with shear rate be 1000s^{- 1}When shearing Viscosity (η₃) the ratio between (η₁/η₃) form calculate.

The ＞ of ＜ comparative examples 1

(passivation layer is formed with the preparation of composition 10)

Oacetic acid aluminum-diisopropoxide 15.0g, above-mentioned ethyl cellulose solution 35.0g and terpineol 30.2g are mixed Close, be prepared into passivation layer formation composition 10.

In addition to using passivation layer formation with composition 10, evaluated similarly to Example 1, shown the result in In table 1.

The ＞ of ＜ comparative examples 2

(passivation layer is formed with the preparation of composition 11)

Oacetic acid aluminum-diisopropoxide 15.1g, isobornyl cyclohexanol 34.9g and terpineol 15.2g are mixed, system It is standby into passivation layer formation composition 11.

In addition to using passivation layer formation with composition 11, evaluated similarly to Example 1, shown the result in In table 1.In addition, thixotropic ratio is with shear rate as 1.0s^{- 1}When shear viscosity (η₁) with shear rate be 1000s^{- 1}When shearing Viscosity (η₃) the ratio between (η₁/η₃) form calculate.

【Table 1】

As known from the above, by using passivation layer formation composition of the invention, can be formed with excellent passivation effect Fruit and the big passivation layer of refractive index.In addition understand, the excellent storage stability of passivation layer formation composition of the invention.And then Understand, by using passivation layer formation composition of the invention, the passivation layer of required shape can be formed with easy operation.

In addition, in disclosure for Japanese patent application 2012-156472 and Japanese patent application 2012-218389 Hold, be incorporated into its entirety as reference in this specification.

Whole documents, patent application and technical standard described in this specification, it is and specific and describe each respectively The situation of document, patent application and technical standard is quoted in this specification with degree as reference.

Claims

1. a kind of passivation layer formation composition, its include organo-aluminum compound shown in following logical formula (I)s and selected from titanium alkoxide, At least one alkanol salt compound in zirconium alkoxides and silicon alkoxide,

In logical formula (I), R¹The alkyl of carbon number 1~8 is separately represented, n represents 0~3 integer, X²And X³Separately Represent oxygen atom or methylene, R²、R³And R⁴Separately represent the alkyl of hydrogen atom or carbon number 1~8.

2. passivation layer formation composition according to claim 1, it also includes alkanol niobium.

3. passivation layer formation composition according to claim 2, wherein, the alkanol niobium is selected from ethanol niobium, isopropyl At least one in alcohol niobium, normal propyl alcohol niobium, n-butanol niobium and phenol niobium.

4. the passivation layer formation composition according to any one of claims 1 to 3, wherein, the alkanol salt compound Including at least the titanium alkoxide, the titanium alkoxide be selected from methyl alcohol titanium, titanium ethanolate, isopropyl titanate, normal propyl alcohol titanium, n-butyl titanium, At least one in tert-butyl alcohol titanium, titanium isobutoxide, diisopropoxy bis-acetylacetonate titanium and four (2- ethyl -1- hexanols) titaniums.

5. the passivation layer formation composition according to any one of Claims 1 to 4, wherein, the alkanol salt compound Including at least the zirconium alkoxides, the zirconium alkoxides are selected from ethanol zirconium, zirconium iso-propoxide, zirconium-n-propylate, zirconium-n-butylate, the tert-butyl alcohol At least one in zirconium, acetylacetone,2,4-pentanedione zirconium, trifluoroacetylacetone (TFA) zirconium and hexafluoroacetylacetone zirconium.

6. the passivation layer formation composition according to any one of Claims 1 to 5, wherein, the alkanol salt compound Including at least the silicon alkoxide, the silicon alkoxide is the silicon alkoxide shown in following logical formula (II)s,

(R⁵O)_(4-m)SiR⁶ _m (II)

In logical formula (II), R⁵And R⁶The alkyl of carbon number 1~8 is separately represented, m represents 0~3 integer.

7. the passivation layer formation composition according to any one of claim 1~6, it also includes resin.

8. the passivation layer formation composition according to any one of claim 1~7, it also includes following logical formula (III)s Shown compound

9. a kind of semiconductor substrate with passivation layer, it has semiconductor substrate and the whole face being arranged on the semiconductor substrate Or the passivation layer of a part, the passivation layer is the heat of the passivation layer formation composition any one of claim 1~8 Processed material.

10. a kind of manufacture method of the semiconductor substrate with passivation layer, it includes：

To the passivation layer formation group any one of the whole face on semiconductor substrate or a part of entitle requirement 1~8 Compound and form the operation of composition layer；With

The composition layer is heat-treated and the operation of passivation layer is formed.

A kind of 11. solar cell devices, it has：

P-type layer and n-layer are carried out the semiconductor substrate of pn engagements；

The whole face being arranged on the semiconductor substrate or the passivation layer of a part, the passivation layer are in claim 1~8 The heat treatment thing of the passivation layer formation composition described in；With

It is configured at the electrode on the layer selected from more than 1 in the p-type layer and n-layer of the semiconductor substrate.

A kind of 12. manufacture methods of solar cell device, it includes：

To more than 1 with the pn-junction for engaging p-type layer and n-layer and in selected from the p-type layer and the n-layer Layer on have electrode face semiconductor substrate, with the electrode at least a portion, entitle requirement 1~8 in Passivation layer formation composition described in any one and form the operation of composition layer；With

A kind of 13. solar cells, it has solar cell device described in claim 11 and is configured at the solar energy Wiring material on the electrode of cell device.