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CN104821337A - A thin film transistor substrate having a passivation film, and a method of manufacturing the same - Google Patents

A thin film transistor substrate having a passivation film, and a method of manufacturing the same Download PDF

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Publication number
CN104821337A
CN104821337A CN201510046590.6A CN201510046590A CN104821337A CN 104821337 A CN104821337 A CN 104821337A CN 201510046590 A CN201510046590 A CN 201510046590A CN 104821337 A CN104821337 A CN 104821337A
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China
Prior art keywords
film transistor
polysiloxanes
diaphragm
thin film
base plate
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CN201510046590.6A
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Chinese (zh)
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CN104821337B (en
Inventor
石河泰明
浦冈行治
野中敏章
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Wisdom Buy
Merck Patent GmbH
Nara Institute of Science and Technology NUC
AZ Electronic Materials Japan Co Ltd
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NAT UNIVERSITY CORP NARA I OF
AZ Electronic Materials Luxembourg SARL
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78606Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06Polymers
    • H01L2924/0715Polysiloxane

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Ceramic Engineering (AREA)
  • Thin Film Transistor (AREA)
  • Silicon Polymers (AREA)
  • Manufacturing & Machinery (AREA)
  • Formation Of Insulating Films (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

The invention provides a thin film transistor substrate having a passivation film and a method of manufacturing the same. The substrate can give high driving stability. A thin film transistor substrate is a thin film transistor substrate which has a thin film transistor and a protective cover formed by cured products of photosensitive siloxane combinations which cover a thin film transistor. The thin film transistor substrate is characterized in that the thin film transistor has a semiconductor layer formed by an oxide semiconductor. The photosensitive siloxane combinations have at least two kinds of polysiloxane which have different alkali dissolution rates, a sensitiser and a solvent.

Description

Possess thin film transistor base plate and the manufacture method thereof of diaphragm
Technical field
The present invention relates to the thin film transistor base plate and manufacture method thereof that possess diaphragm.
Background technology
In recent years, take high resolution display as direction, developing a kind of employing with the thin-film transistor of the amorphous state InGaZnO oxide semiconductor that is representative actively.About oxide semiconductor, compare with the amorphous silicon film transistor used in a liquid crystal display, electron mobility is large, demonstrates the electrical characteristics of the excellences such as large ON/OFF ratio, thus expects the driving element, the province's electric device that become OLED display.Towards in the exploitation of display, particularly keep becoming important problem as the equipment running stability of transistor and uniformity on large area substrates.As extremely important key element for equipment running stability, have protection oxide semiconductor layer not by the dielectric film of the infringement of external environment condition.But, as such dielectric film, mainly use in the past employ the protection dielectric film (patent documentation 1 and 2) utilized in the thin-film transistor of amorphous silicon, likely do not give full play to oxide semiconductor physical property inherently.And, can think that this becomes the one of the main reasons of the limited performance of the thin-film transistor employing oxide semiconductor.
Diaphragm in oxide semiconductor must be the diaphragm of the intrusion suppressing moisture, hydrogen, oxygen etc.The intrusion of these impurity changes the conductivity of oxide semiconductor significantly, hinders the running stability such as the variation of threshold value.From the viewpoint; about protection dielectric film in the past, be mainly suitable for SiOx, SiNx, SiONx etc. of obtaining by utilizing the physical vaporous depositions (PVD) such as chemical vapour deposition technique (CVD), sputtering with individual layer or multilayer.Go out the manufacturing process such as the CVD of the inoranic membrane of these high barriers for film forming and likely damage is caused to the basalis (i.e. oxide semiconductor) of the thin-film transistor employing oxide semiconductor.Specifically, the diaphragm in the past formed out as utilizing vacuum deposition apparatus, has SiO 2film, SiN film, but unstrpped gas is decomposed and film forming by utilizing plasma etc. by these films, thus in this manufacture craft, have the ion species produced by plasma and damage is caused to oxide semiconductor surface, make membrane property that the situation of deterioration occur.In addition, when manufacture oxide-semiconductor devices, likely cause oxide semiconductor deteriorated further because of techniques such as various chemical solution, dry etchings.Therefore, as not by the protection of the injury of operation, the diaphragms (patent documentation 3) such as etching barrier film have been suitable in the lump.
In addition, when employ such take gas as the film build method of raw material, when making the display of large-screen, not easily film forming goes out uniform diaphragm.Therefore, in order to solve such problem, proposing and utilizing rubbing method and film forming goes out diaphragm.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2013-211410 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2013-207247 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2012-235105 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2013-89971 publication
Non-patent literature
Non-patent literature 1:Juan Paolo Bermundo, Yasuaki Ishikawa, HarukaYamazaki, Toshiaki Nonaka, Yukiharu Uraoka, " Effect of polysilsesquioxanepassivation layer on the dark and illuminated negative bias stress of amorphousInGaZnO thin-film transistors ", 60th time Applied Physics association disquisition in spring can give a lecture preliminary draft collection, on March 29th, 2013, 29p-F 1-5
Non-patent literature 2:Juan Paolo Bermundo, Yasuaki Ishikawa, HarukaYamazaki, Toshiaki Nonaka, Yukiharu Uraoka, " Effect of reactive ion etchingand post-annealing conditions on the characteristics and reliability of a-InGaZnOthin-film transistors with polysilsesquioxane based passivation layer ", The 13thInternational Meeting on Information Display (IMID) gives a lecture preliminary draft collection, on August 26th, 2013, 431 pages (P2-30)
Summary of the invention
The problem solved is wanted in invention
But; in the diaphragm formation solution used in all the time such rubbing method, mainly include polyimide resin, acrylic resin, the film using this solution to be formed cannot be annealed at high temperature; thus mostly cannot play sufficient performance, leave the leeway of improvement.In addition; also proposed a kind of application type diaphragm (patent documentation 4) employing silicone resin; but in the publication; although the semiconductor element having this diaphragm shows the transistor characteristic at initial stage; but do not carry out open fully for driving stability, can think the leeway having improvement.Propose following method in addition: use silicone resin as application type diaphragm; by the oxide-semiconductor devices utilizing dry etching to add diaphragm to deteriorate man-hour under oxygen atmosphere with 300 DEG C of annealing 2 hours; thus recover semiconductor element characteristic, the element (non-patent literature 1 and 2) that fabrication reliability is high.But the long term annealing of the semiconductor element under the method utilizing dry etching to process diaphragm, high temperature is high cost, also has the leeway of further improveing in addition from the viewpoint of production efficiency.
The present inventor discusses the method solving problem as described above; obtain following opinion: easy method can be utilized, form by the photosensitive siloxane composition containing different at least two kinds of polysiloxanes, emulsion and the solvent of alkali dissolution velocity the thin film transistor base plate possessing diaphragm.Obtain following opinion further: possess in the thin film transistor base plate of diaphragm at such, the deterioration of thin-film transistor can be suppressed, milder annealing can be utilized and give thin film transistor base plate with high driving stability.The present invention is based on relevant opinion and complete.
Therefore, the object of the present invention is to provide a kind of thin film transistor base plate, it is the thin film transistor base plate possessing diaphragm, and can give high driving stability.
In addition; another object of the present invention is to provide a kind of manufacture method possessing the thin film transistor base plate of diaphragm; this manufacture method carries out the processing of diaphragm by exposure imaging, can give thin-film transistor with high driving stability further by the annealing of thin film transistor base plate.
For the scheme of dealing with problems
An embodiment of the invention provide a kind of thin film transistor base plate; it is the thin film transistor base plate of the diaphragm comprising thin-film transistor and formed by the solidfied material of the photosensitive siloxane composition covering aforementioned film transistor; it is characterized in that; aforementioned film transistor has the semiconductor layer formed by oxide semiconductor, and photosensitive silicone composition contains alkali dissolution velocity different at least two kinds of polysiloxanes, emulsion and solvent.
In addition, according to the preferred embodiment of the present invention, provide the above-mentioned thin film transistor base plate formed by photosensitive siloxane composition, about this photosensitive siloxane composition, above-mentioned polysiloxanes comprises polysiloxanes (I) and polysiloxanes (II)
This polysiloxanes (I) is that the silane compound that makes to be represented by following formula (1) under the existence of base catalyst is hydrolyzed with the silane compound represented by following formula (2) and condensation and the polysiloxanes that obtains, and the film after prebake conditions dissolves in 5 % by weight tetramethylammonium hydroxide aqueous solutions, and its dissolution velocity is below/second,
RSi(OR 1) 3(1)
Si(OR 1) 4(2)
In formula, R represents the aryl of the carbon number 6 ~ 20 that the straight-chain of the carbon number 1 ~ 20 that the straight-chain of carbon number 1 ~ 20, branched or cyclic alkyl or at least one methylene also can be replaced by oxygen, the aryl of branched or cyclic alkyl or carbon number 6 ~ 20 or at least one hydrogen also can replaced by fluorine, R 1represent the alkyl of carbon number 1 ~ 5,
This polysiloxanes (II) under the existence of acid or base catalyst, at least makes the silane compound of aforementioned formula (1) be hydrolyzed and condensation and the polysiloxanes that obtains, and the film after prebake conditions dissolves in 2.38 % by weight tetramethylammonium hydroxide aqueous solutions, and its dissolution velocity is more than/second.
Other execution mode of the present invention provides the manufacture method of above-mentioned thin film transistor base plate, and this manufacture method comprises following operation:
Prepare the operation of the photosensitive siloxane composition containing different at least two kinds of polysiloxanes, emulsion and the solvents of alkali dissolution velocity,
Photosensitive silicone composition is coated thin-film transistor, aforementioned solvents drying is formed the operation of diaphragm precursor layer,
By the operation of aforementioned diaphragm precursor layer exposure,
By the operation that the aforementioned diaphragm precursor layer exposed develops,
The aforementioned diaphragm precursor layer developed is heating and curing and forms the operation of diaphragm,
Be heating and curing possessing and the thin-film transistor of the aforementioned diaphragm the obtained operation of annealing at least one times.
The effect of invention
The present invention can provide a kind of relative to voltage stress, photostress, light/voltage stress and show high stability, the thin film transistor base plate that possesses diaphragm.In application type diaphragm in the past, be very difficult by being high stability imparting thin-film transistor relative to stress.In addition, according to the present invention, the thin-film transistor can stablizing running more easily can be realized.And not necessarily vacuum plant etc., thus also can boost productivity significantly.
Accompanying drawing explanation
Fig. 1 represents the ideograph possessing an execution mode (embodiment 1) of the thin film transistor base plate of diaphragm of the present invention.
Fig. 2 represents the ideograph possessing another execution mode of the thin film transistor base plate of diaphragm of the present invention.
Fig. 3 represents the ideograph possessing another execution mode of the thin film transistor base plate of diaphragm of the present invention.
Fig. 4 is the curve chart of the transmission characteristic representing thin film transistor base plate of the present invention.
Fig. 5 is the curve chart of the performance recovery based on annealing of the thin film transistor base plate representing comparative example 2.
Fig. 6 is the curve chart of the transmission characteristic of the thin film transistor base plate representing comparative example 2.
Fig. 7 is the curve chart of the performance recovery based on annealing of the thin film transistor base plate representing reference example 1.
Fig. 8 is the curve chart of the transmission characteristic of the thin film transistor base plate representing reference example 1.
Fig. 9 is the curve chart of the performance recovery based on annealing of the thin film transistor base plate representing reference example 2.
Embodiment
About embodiments of the present invention, reference accompanying drawing is while explain as follows.
First, Fig. 1 shows and utilizes manufacture method of the present invention and an execution mode of the thin film transistor base plate 1 possessing diaphragm formed out.In FIG, on grid layer 2, be formed with gate insulator 3, be formed with metal oxide semiconductor layer 4 thereon.Form source electrode 5 at the two ends of metal oxide semiconductor layer 4 respectively according to the mode connected with gate insulator 3 further and drain 6.In addition, although do not illustrate, etching barrier film also can be formed on metal oxide semiconductor layer 4.Diaphragm 7 according to cover these metal oxide semiconductor layers 4, source electrode 5 and drain electrode 6 mode formed.As other execution mode; such as; also can similarly be suitable for: there is the source electrode 5 that to define via the contact hole (contact hole) 9 on diaphragm 7 and contact with oxide semiconductor layer 4 and drain 6 the thin film transistor base plate (Fig. 2) of structure, or the thin film transistor base plate of top gate structure.In addition, structure shown here is only the structure exemplified, manufacturing method according to the invention, also can manufacture have shown here outside the thin film transistor base plate of structure.
Fig. 3 illustrates an execution mode of the thin film transistor base plate defining pixel electrode 8 on diaphragm 7.Via the contact hole 9 being formed at diaphragm, pixel electrode 8 is contacted with drain electrode 6.
[possessing the thin film transistor base plate of diaphragm]
The diaphragm that thin film transistor base plate of the present invention comprises thin-film transistor and formed by the solidfied material of the silicone composition of cover film transistor.Thin film transistor base plate of the present invention also can possess multiple diaphragm, also can have the second diaphragm on the diaphragm covered by thin-film transistor.In this manual, thin-film transistor refers to that the element forming thin film transistor base plate is all, and this thin film transistor base plate is such as substrate having electrode, circuit, semiconductor layer and insulating barrier etc. etc. on surface.In addition, as the distribution be configured on substrate, list gate wirings, data wiring, for connecting via (via) distribution etc. of two or more wiring layers.As semiconductor layer, be generally amorphous silicon, polysilicon semiconductor and oxide semiconductor.About the thin film transistor base plate possessing diaphragm of the present invention, particularly from the viewpoint of oxide semiconductor and obtain high protective feature by annealing process, be preferred.In the past, in order to can high annealing be carried out, be thus suitable for utilize PE-CVD method and the inoranic membrane of the silicon oxide layer, silicon nitride etc. that are formed out as diaphragm, but in order to form contact hole on these inoranic membranes, thus must carry out reactive ion etching etc.But the deterioration of reactive ion etching accelerating oxidation thing semiconductor significantly, thus after processing in order to recover the performance of semiconductor, needs to improve annealing temperature described later.In the present invention, diaphragm suppresses the deterioration of semiconductor, can utilize milder annealing and give thin-film transistor with high driving stability.
About the diaphragm in thin film transistor base plate of the present invention, formed by the photosensitive siloxane composition containing different at least two kinds of polysiloxanes, emulsion and the solvent of alkali dissolution velocity.By using such photosensitive siloxane composition; thus can exposure imaging be utilized and carry out the processing of diaphragm; do not utilize dry etching etc. and to carry out pattern processing also harmless, therefore tool has the following advantages: smaller to the damage of thin-film transistor performance, and annealing time is short also harmless.For such photosensitive siloxane composition, be described in detail following.
[photosensitive siloxane composition]
Photosensitive siloxane composition is categorized as positive type photo-sensitive siloxane composition and negative-type photosensitive silicone composition according to the kind of emulsion.The preferred positive type photo-sensitive siloxane composition used in order to the diaphragm formed in thin film transistor base plate of the present invention contains the different at least two kinds of polysiloxanes (I) of alkali dissolution velocity and (II), as the diazo-naphthalene-based quinone derivative of emulsion and solvent.About such positive type photo-sensitive siloxane composition, by making exposure portion become alkaline soluble developer solution, utilizing development and removing, thus forming positive type light sensitive layer.On the other hand; feature for the formation of the preferred negative-type photosensitive silicone composition of the diaphragm in thin film transistor base plate of the present invention is, comprises the different at least two kinds of polysiloxanes (I) of alkali dissolution velocity and (II), the auxiliary curing agent that can produce acid or alkali under the effect of light and solvent form.About such negative-type photosensitive silicone composition, remain after development by making exposure portion become to be insoluble to alkaline developer, thus form negative photosensitive layer.
< polysiloxanes >
The polymer that it is main chain that polysiloxanes refers to Si-O-Si key (siloxane bond).In addition in this manual, in polysiloxanes, also comprise by general formula (RSiO 1.5) nthe silsesquioxane polymer represented.
In the present invention, as in order to form polysiloxanes contained in photosensitive siloxane composition that diaphragm uses, preferably at least two kinds of polysiloxanes that alkali dissolution velocity is different are used.As the polysiloxanes that such alkali dissolution velocity is different, preferably use following polysiloxanes (I) and (II).Polysiloxanes (I) is, makes the silane compound that represented by following formula (1) and the silane compound represented by following formula (2) be hydrolyzed and condensation and the polysiloxanes that obtains under the existence of base catalyst.Film after the prebake conditions of polysiloxanes (I) dissolves in 5 % by weight TMAH solution, and its dissolution velocity is below/second, be preferably / second.Dissolubility is when more than/second, the possibility of residual insoluble matter becomes extremely low after development, is preferred preventing in broken string etc.
RSi(OR 1) 3(1)
Si(OR 1) 4(2)
In formula, R represents the aryl of the carbon number 6 ~ 20 that the straight-chain of the carbon number 1 ~ 20 that the straight-chain of carbon number 1 ~ 20, branched or cyclic alkyl or at least one methylene also can be replaced by oxygen, the aryl of branched or cyclic alkyl or carbon number 6 ~ 20 or at least one hydrogen also can replaced by fluorine, R 1represent the alkyl of carbon number 1 ~ 5.
Polysiloxanes (II) is, at least makes the silane compound of general formula (1) be hydrolyzed and condensation and the polysiloxanes that obtains under the existence of acid or base catalyst.Film after the prebake conditions of polysiloxanes (II) dissolves in the 2.38 % by weight TMAH aqueous solution, and its dissolution velocity is more than/second, be preferably / second.About the dissolution velocity of polysiloxanes (II), according to the thickness of the diaphragm as target, can be / second extremely the scope of/second is selected.More preferably / second extremely / second.By being set to below/second, make with the dissolution velocity difference of polysiloxanes (I) not excessive, can develop uniformly.
About polysiloxanes (I), the pattern after development not easily causes " pattern " to subside when being heating and curing, but alkali-solubility is extremely little, thus cannot be used alone.In addition; even if in order to be used alone polysiloxanes (I) or polysiloxanes (II) and adjust alkali-solubility; also cannot obtaining in the present invention in order to form the stability of pattern such shown in photosensitive siloxane composition that diaphragm uses, thus preferably polysiloxanes (I) and (II) being carried out combining and uses.In addition, when dissolution velocity difference is large, preferably the wide variety of silicone (II) that dissolution velocity is different is used.
About the content of the silane compound of the aforementioned formula (2) in above-mentioned polysiloxanes (I) and polysiloxanes (II), suitably can set according to purposes, but in each polysiloxane compound, be preferably 3mol% ~ 40mol%, the hardness of controlling diaphragm, pattern heat-staple in be more preferably 5mol% to 30mol%.By making this content be more than 3mol%, thus the pattern stability under high temperature becomes better, by being below 40mol%, thus suppresses reactivity, makes stability when storing become better.
Mensuration, the computational methods > of < alkali dissolution velocity (ADR)
About polysiloxanes (I) and (II) to the dissolution velocity of the TMAH aqueous solution, measure as described below and calculate.
First, polysiloxanes is dissolved in propylene glycol methyl ether acetate (PGMEA) according to the mode becoming about 35 % by weight.This solution is become the mode rotary coating of the thickness of about 2 μm according to dry film thickness on Silicon Wafer, on the hot plate of 100 DEG C, carry out thereafter heating in 60 seconds thus remove solvent further.Utilize light splitting elliptic polarization spectrometer (Woollam society), carry out the determining film thickness of coated film.Then, for the Silicon Wafer with this film, the 5%TMAH aqueous solution is immersed in room temperature (25 DEG C) when polysiloxanes (I), when polysiloxanes (II), be immersed in the 2.38%TMAH aqueous solution in room temperature (25 DEG C), measure the time till overlay film disappears.Dissolution velocity is by obtaining initial stage thickness divided by the time till overlay film disappearance.When dissolution velocity is significantly slow, carry out the determining film thickness after submergence certain hour, by the Thickness Variation amount before and after submergence divided by Immersion time, calculate dissolution velocity.
In any one polymer in polysiloxanes (I), (II), the weight average molecular weight of polystyrene conversion is all generally 700 ~ 10, and 000, be all preferably 1,000 ~ 4,000.If molecular weight is in above-mentioned scope, then obtain sufficient resolution by the generation of the residual error that prevents from developing, photosensitivity also becomes good, is thus preferably adjusted in above-mentioned scope by molecular weight.
About the mixed proportion of polysiloxanes (I), (II), can adjust with arbitrary ratio according to the photosensitivity of the thickness of interlayer dielectric, photosensitive composite, resolution etc., but there is " pattern " in being heating and curing to subside preventing effectiveness by the polysiloxanes (I) that comprises more than 20 % by weight, thus preferably." pattern " subsides and refers to following phenomenon herein: when being heated by pattern, pattern deforms, and such as, section is rectangle and crest line is clear and definite pattern ridgeline portions change circle after heating, or the side being close to vertical rectangular shape becomes inclination.
< emulsion >
About the photosensitive siloxane composition being formed pattern by light in the present invention, comprise various emulsion as its composition.As the emulsion used in positive type photo-sensitive siloxane composition, list diazo-naphthalene-based quinone derivative, as the emulsion used in negative-type photosensitive silicone composition, list and then occur to decompose when irradiating light and promote the auxiliary curing agent of the condensation of silanol group.Below, respective emulsion is described.
< diazo-naphthalene-based quinone derivative >
Diazo-naphthalene-based quinone derivative in the present invention is that naphthoquinones diazido sulfonic acid (naphthoquinone diazido sulfonic acid) is incorporated into the compound with phenolic hydroxyl group and the compound obtained with ester bond, structurally be not particularly limited, but be preferably the ester compounds with the compound with more than 1 phenolic hydroxyl group.As naphthoquinones diazido sulfonic acid, 4-naphthoquinones diazido sulfonic acid or 5-naphthoquinones diazido sulfonic acid can be used.4-naphthoquinones diazido sulfonate compound has absorption in i line (wavelength 365nm) region, is therefore suitable for i line exposing.In addition, there is absorption in the wave-length coverage of wide scope in 5-naphthoquinones diazido sulfonate compound, is thus suitable for the exposure carried out under the wavelength of wide scope.4-naphthoquinones diazido sulfonate compound, 5-naphthoquinones diazido sulfonate compound is preferably selected according to the wavelength exposed.Also 4-naphthoquinones diazido sulfonate compound can be mixed with 5-naphthoquinones diazido sulfonate compound and use.
As the compound with phenolic hydroxyl group, be not particularly limited, such as, list following compound (trade name, Honshu Chemical Ind's system).
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
About the addition of diazo-naphthalene-based quinone derivative, dissolving according to the esterification yield of naphthoquinones diazido sulfonic acid or the physical property of the polysiloxanes that uses, required photosensitivity, exposure portion and unexposed portion contrasts, and make optimal amount have difference, but as interlayer dielectric of the present invention, be preferably relative to polysiloxane mixture 100 weight portion, be 3 ~ 20 weight portions, more preferably 5 ~ 15 weight portions.When the addition of diazo-naphthalene-based quinone derivative is more than 3 weight portions, then the dissolving in exposure portion and unexposed portion contrasts and uprises, and has good photonasty.In addition, more than 5 weight portions are preferably in order to obtain better dissolving contrast.On the other hand, when the addition of diazo-naphthalene-based quinone derivative is below 20 weight portions, then improve the colorless transparency of cured film.
< auxiliary curing agent >
As the auxiliary curing agent used in the present invention, have and then occur to decompose when irradiating light and promote the auxiliary curing agent of the condensation of silanol group.List and discharge as making composition carry out the light acid producing agent of the acid of the active material of photocuring, discharge the light alkali generation agent etc. of alkali.Herein, as light, visible ray, ultraviolet can be listed, or infrared ray etc.Particularly, preferably utilize the ultraviolet used in the manufacture of thin-film transistor and produce the auxiliary curing agent of acid or alkali.
About the addition of auxiliary curing agent, decompose according to auxiliary curing agent and the kind of active material, generation, required photosensitivity, the exposure portion that produce contrast from the dissolving in unexposed portion and it is different that optimal amount is had, but relative to polysiloxane mixture 100 weight portion, be preferably 0.001 ~ 10 weight portion, more preferably 0.01 ~ 5 weight portion.When addition is more than 0.001 weight portion, then the dissolving in exposure portion and unexposed portion contrasts and uprises, and additive effect becomes good.On the other hand, if the addition of auxiliary curing agent is below 10 weight portions, so suppress to the crackle in the overlay film formed, that also suppresses to cause because of the decomposition of auxiliary curing agent is painted, thus improves the colorless transparency of overlay film.
As the example of light acid producing agent, list diazomethane compound, diphenyl iodnium, triphenyl sulfonium salt, sulfonium salt, ammonium salt, phosphonium salt, sulfonyl imide compounds etc.The structure of these light acid producing agents can be represented by general formula (A).
R +X -(A)
Herein, R +represent the organic ion selected from the group be made up of alkyl, aryl, thiazolinyl, acyl group and the alkoxyl modified by hydrogen, carbon atom or other hetero-atom, such as, diphenyl iodide ion, triphenylsulfonium ion.
In addition, X -any one counter ion counterionsl gegenions preferably represented by following general formula.
SbY 6 -
AsY 6 -
R a pPY 6-p -
R a qBY 4-q -
R a qGaY 4-q -
R aSO 3 -
(R aSO 2) 3C -
(R aSO 2) 2N -
R bCOO -
SCN -
In formula, Y is halogen atom, R athe alkyl of carbon number 1 ~ 20 that be instead of by the substituting group selected from fluorine, nitro and cyano group or the aryl of carbon number 6 ~ 20, R bbe the alkyl of hydrogen or carbon number 1 ~ 8, p is the numerical value of 0 ~ 6, and q is the numerical value of 0 ~ 4.
As concrete counter ion counterionsl gegenions, list from by BF 4 -, (C 6f 5) 4b -, ((CF 3) 2c 6h 3) 4b -, PF 6 -, (CF 3cF 2) 3pF 3 -, SbF 6 -, (C 6f 5) 4ga -, ((CF 3) 2c 6h 3) 4ga -, SCN -, (CF 3sO 2) 3c -, (CF 3sO 2) 2n -, formate ion, acetate ion, trifluoromethanesulfonic acid radical ion, nine fluorine butane sulfonate ions, tosylate ion, butane sulfonate ion, benzenesulfonate ion, p-methyl benzenesulfonic acid radical ion and sulfonate ion composition group in the counter ion counterionsl gegenions selected.
Among the light acid producing agent used in the present invention, particularly, the light acid producing agent producing sulphonic acids or boric acid class is good, such as, list: tolylcumyl iodine four (pentafluorophenyl group) boric acid (Rhodia Inc. PHOTOINITIATOR2074 (trade name)), diphenyl iodine four (perfluorophenyl) boric acid, cation portion are made up of sulfonium cation and the material etc. that is made up of five fluoro boron acid ions of anion portion.In addition, list triphenylsulfonium triflate sulfonic acid, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium four (perfluorophenyl) boric acid, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoroarsenate, 1-(4-n-butoxy naphthalene-1-base) thiophane trifluoromethanesulfonic acid, 1-(4,7-dibutoxy-1-naphthyl) thiophane trifluoromethanesulfonic acid, diphenyl iodine trifluoromethanesulfonic acid, diphenyl iodine hexafluoroarsenate etc.Further, the light acid producing agent represented by following formula can also be used.
[chemical formula 4]
In formula, the substituting group of A separately for selecting from the aryl carbonyl of the alkyl-carbonyl of the aryl of the alkoxyl of the alkyl of carbon number 1 ~ 20, carbon number 1 ~ 20, carbon number 6 ~ 20, carbon number 1 ~ 20, carbon number 6 ~ 20, hydroxyl and amino, p is separately the integer of 0 ~ 5, B -list the alkyl azochlorosulfonate group fluoridized, the aryl sulfonic acid foundation group of having fluoridized, the boron alkyl sulfonate groups fluoridized, alkyl azochlorosulfonate group, aryl sulfonic acid foundation group etc.Also can use: the compound that the cation shown in these formulas and anion are mutually exchanged and obtain, the light acid producing agent that the cation shown in these formulas or anion and aforesaid various cation or anion are carried out combining and obtain.Such as, any one in the sulfonium cation illustrated by formula and four (perfluorophenyl) borate ion carried out combining and the material obtained, any one in the iodide ion illustrated by formula and four (perfluorophenyl) borate ion carried out combining and the material obtained also can be used as light acid producing agent.
Produce the example of agent as aforementioned smooth alkali, list polysubstituted amide compound, lactams, imide analog compounds or the light alkali that comprises this structure with amide groups and produce agent.
The example of agent is produced as aforementioned thermokalite, list the imdazole derivatives, 1 such as N-(2-nitrobenzyloxycarbonyl) imidazoles, N-(3-nitrobenzyloxycarbonyl) imidazoles, N-(4-nitrobenzyloxycarbonyl) imidazoles, N-(5-methyl-2-nitrobenzyloxycarbonyl) imidazoles, N-(the chloro-2-nitrobenzyloxycarbonyl of 4-) imidazoles, 8-diazabicyclo (5,4,0) 11 carbon-7-alkene, tertiary amines, quaternary ammonium salt, their mixture.It is same with acid producing agent that these alkali produces agent, can be used alone or used in combination.
< solvent >
As solvent, such as list glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, the ethylene glycol monoalkyl ether classes such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, the diethylene glycol dialkyl ether classes such as dibutyl ethylene glycol ether, methylcellosolve acetate, the ethylene glycol alkylether acetates classes such as ethyl cellosolve acetate, PGMEA, propylene glycol monoethyl ether acetate, the propylene glycol alkyl ether acetic acid ester classes such as propylene glycol monopropyl ether acetic acid esters, benzene, toluene, dimethylbenzene etc. are aromatic hydrocarbon based, methylethylketone, acetone, methyl amyl ketone, methyl iso-butyl ketone (MIBK), the ketones etc. such as cyclohexanone.These solvents separately use, or combine two or more and use.About the compounding ratio of solvent, different according to the requirement of thickness after coating process, coating.Such as, when spraying coating, with the total weight of polysiloxanes and arbitrary composition for benchmark, be set to more than 90 % by weight, but in the slit of the large-size glass substrate used in the manufacture of display coating (slit coat), be generally more than 50 % by weight, be preferably more than 60 % by weight, be generally less than 90 % by weight, be preferably less than 85 % by weight.
< optional member >
In addition, photosensitive siloxane composition of the present invention also can comprise other optional member as required.As such composition, list surfactant etc.
Among them, preferably use surfactant to improve coating.As surfactant operable in the photosensitive siloxane composition in the present invention, such as, list nonionic class surfactant, anionic based surfactants, amphoteric surfactant etc.
As above-mentioned nonionic class surfactant, such as list: polyethylene oxide alkyl ethers is polyoxyethylene lauryl ether such as, polyethylene glycol oxide oleyl ether, the polyethylene oxide alkyl ethers classes such as polyoxyethylene cetyl ethers, polyethylene glycol oxide fatty acid diesters, polyethylene glycol oxide fatty-acid monoester, polyethylene glycol oxide polyoxypropylene block polymer, acetylene alcohol, acetylenic glycols, the APEO of acetylene alcohol, the acetylenic glycols derivatives such as the APEO of acetylenic glycols, fluorine-containing surfactant is Fluorad (trade name such as, Sumitomo 3MLimited system), Megafac (trade name, Dainippon Ink Chemicals's system), Surflon (trade name, Asahi Glass Co., Ltd's system), or organosiloxane surfactant is KP341 (trade name such as, Shin-Etsu Chemial Co., Ltd's system) etc.As aforementioned acetylenic glycols, list 3-methyl isophthalic acid-butine-3-alcohol, methylpentynol, 3,6-dimethyl-4-octynes-3,6-glycol, 2,4,7,9-tetramethyl-5-decine-4,7-glycol, 3,5-dimethyl-1-hexin-3-alcohol, 2,5-dimethyl-3-hexin-2,5-glycol, 2,5-dimethyl-2,5-hexane diol etc.
In addition, as anionic based surfactants, list the ammonium salt or organic amine salt etc. of the ammonium salt of alkyl diphenyl base ether disulfonic acid or organic amine salt, the ammonium salt of alkyl diphenyl base ether sulfonic acid or organic amine salt, the ammonium salt of alkyl benzene sulphonate or organic amine salt, the ammonium salt of polyethylene oxide alkyl ethers sulfuric acid or organic amine salt, alkylsurfuric acid.
Be further used as amphoteric surfactant, list 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole betaine, dodecanamide propyl hydroxyl sulfo betaine etc.
These surfactants can use individually or mix two or more and use, and about its compounding ratio, relative to the total weight of photosensitive siloxane composition, are generally 50 ~ 10,000ppm, are preferably 100 ~ 5,000ppm.
[possessing the manufacture method of the thin-film transistor of diaphragm]
Photosensitive siloxane composition is coated thin-film transistor, heats, thus obtain the thin film transistor base plate possessing diaphragm (cured film).Now, carry out via desired mask exposing, developing, thus form the pattern of contact hole etc.
As the manufacture method of thin film transistor base plate with oxide semiconductor layer, enumerate the TFT of the bottom gate type shown in Fig. 1 as an example, and be described.On the substrate utilizing glass etc., pattern forms out grid 2.As grid material, molybdenum, aluminium and aluminium alloy, copper and the material such as copper alloy, titanium are formed in the mode of individual layer or two or more stacked films.Grid is formed gate insulating film 3.As gate insulating film, generally speaking utilize PE-CVD method and form silicon oxide layer, silicon nitride film, silicon nitriding and oxidizing film etc.The thickness of gate insulating film is generally 100 to 300nm.About the oxide semiconductor layer 4 on gate insulating film, have following method: utilize DC sputtering or RF to sputter the composition sputtering target identical with oxide semiconductor and carry out the sputtering method of film forming; And the precursor solution of metal alkoxide, metal organic acid salt, chloride etc., the dispersion liquid of oxide semiconductor nano particle are carried out being coated with and roasting, thus form the liquid phase method of oxide semiconductor layer.After having carried out the pattern formation of oxide semiconductor layer 4, pattern has formed out source/drain 5 and 6.About source/drain material, molybdenum, aluminium and aluminium alloy, copper and the material such as copper alloy, titanium are formed in the mode of individual layer or two or more stacked films.
About the manufacture method of thin film transistor base plate possessing diaphragm; the thin-film transistor with above-mentioned oxide semiconductor layer is coated with photosensitive siloxane composition and utilizes prebake conditions etc. to carry out drying; then expose; by tetramethylammonium hydroxide aqueous solution (generally speaking; use 2.38% aqueous solution) carry out developing and define the pattern of contact hole etc., be then coated with photosensitive siloxane composition (diaphragm precursor layer) is cured and forms diaphragm 7.Further, diaphragm such as forms ito film by sputtering method, carry out patterning thus the element of formation Fig. 3.In addition, on this diaphragm, also can utilize CVD, PVD and define inoranic membrane, or also can have organic material for the object of diaphragm, leveling utilizes rubbing method.
Each operation of manufacture method of the present invention is below described.
< prepares the operation > of photosensitive siloxane composition
Possess in the manufacture method of the thin film transistor base plate of diaphragm of the present invention, prepare the photosensitive siloxane composition containing different at least two kinds of polysiloxanes, emulsion and the solvents of alkali dissolution velocity.The details of each constituent of photosensitive siloxane composition is as above-mentioned.
< painting process >
About the painting process in the present invention, by above-mentioned photosensitive siloxane composition is coated film crystal tube-surface to carry out.About this painting process, undertaken by general coating process, that is, by submergence coating, roller coat, scraper coating, brush, spraying coating, scraper for coating, flow coat, spin coating, slit coating etc., the coating process as photosensitive composite in the past and known any means is carried out.Coating more than twice and be coated with once or repeatedly as required, thus diaphragm precursor layer can be made desired thickness.
< prebake conditions operation >
After defining diaphragm precursor layer, this layer is dry further, and in order to reduce solvent residual amount, thus preferred this layer is carried out prebake conditions (heat treated).About prebake conditions operation, generally the temperature of 70 ~ 150 DEG C, preferably the temperature of 90 ~ 130 DEG C, 10 ~ 180 seconds can be implemented when carrying out based on hot plate, preferably can implementing 30 ~ 90 seconds, 1 ~ 5 minute can be implemented when carrying out based on cleaning oven.The removal of solvents operation based on rotation, vacuum was preferably comprised before prebake conditions.
< exposure process >
After defining diaphragm precursor layer, illumination is carried out to its surface and penetrates.Hit the light source of use about illumination, the arbitrary light source in the past used in pattern formation method can be used.As such light source, the lamp of high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, metal halide, xenon etc., laser diode, LED etc. can be listed.As irradiation light, usually use the ultraviolets such as g line, h line, i line.Except the superstructure technologies that semiconductor is such, in the patterning of several μm to tens of μm, generally use the light (high-pressure mercury-vapor lamp) of 360 ~ 430nm.Wherein, the light of 430nm is mostly used when liquid crystal indicator.Irradiate the energy of light also relevant with the thickness of light source, diaphragm precursor layer, but when the eurymeric of generally speaking diazo-naphthalene-based quinone derivative, be set to 20 ~ 2000mJ/cm 2, be preferably set to 50 ~ 1000mJ/cm 2.Irradiate luminous energy lower than 20mJ/cm 2shi Ze cannot obtain sufficient resolution sometimes, on the contrary higher than 2000mJ/cm 2time, then have exposure and become too much, cause the situation of the generation of halation.In addition, when minus, 1 ~ 500mJ/cm is set to 2, be preferably set to 10 ~ 100mJ/cm 2.Irradiate luminous energy lower than 1mJ/cm 2time then film to reduce degree (film thinning) large, on the contrary higher than 500mJ/cm 2time, then expose and become too much sometimes, cannot resolution be obtained sometimes.
In order to pattern-like irradiate light, general photomask can be used.Such photomask can be selected arbitrarily from known photomask.Environment when irradiation is not particularly limited, but is generally speaking set to surrounding environment (in air), nitrogen environment.In addition, when whole of substrate surface forms film, illumination is carried out to the whole face of substrate surface and penetrates.In the present invention, about pattern film, be also included within the situation that the whole face of such substrate surface defines film.
Heating process > after < exposure
After exposure, promoting to react between the polymer in film to utilize at the exposure reaction initiator that produces of position, thus can carry out exposing rear heating (PostExposure Baking) as required.About this heat treated; it not the heat treated of carrying out in order to diaphragm precursor layer is fully solidified; but according to can only make desired pattern residue on substrate after development, the heat treated that the mode that its outer part can be removed by developing is carried out.
< developing procedure >
After exposure, after carrying out exposing rear heating as required, development treatment is carried out to diaphragm precursor layer.As the developer solution used when development, the in the past known arbitrary developer solution used in the development of photosensitive siloxane composition can be used.In the present invention, in order to specific go out polysiloxanes dissolution velocity and use Tetramethylammonium hydroxide (TMAH) aqueous solution, but when forming cured film, the developer solution that uses is not limited to this.As preferred developer solution, list the aqueous solution of the alkali compounds such as tetra-alkyl ammonium hydroxide, choline, alkali metal hydroxide, alkali metal silicate (hydrate), alkali metal phosphate (hydrate), ammonia, alkylamine, alkanolamine, hetero ring type amine, i.e. alkaline developer, particularly preferred alkaline developer is the TMAH aqueous solution.In these alkaline developers, also can comprise the water-miscible organic solvent such as methyl alcohol, ethanol or surfactant further as required.Developing method also can be selected arbitrarily from the past known method.Specifically list to the dipping (dip) in developer solution, revolve and cover submergence (puddle), shower, slit coating (slit), method such as bell-type coating (cap coat), spraying etc.By this development, pattern can be obtained.Utilized developer solution to carry out development after, preferably wash.In addition, in manufacture method of the present invention, as shown in Figure 3, also can via the contact hole 9 formed out by developing, by drain electrode 6 and transparency electrode (pixel electrode 8) conducting be formed on diaphragm 7.
Irradiation process > after < development
Use the composition of eurymeric, when the diaphragm formed is used as hyaline membrane, the illumination preferably carrying out being called bleaching exposure (bleaching exposure) is penetrated.By carrying out bleaching exposure, thus unreacted diazo-naphthalene-based quinone derivative generation photodissociation residual in film, therefore improve the optical transparency of film further.As the method for bleaching exposure, use high-pressure mercury-vapor lamp, Cooper-Hewitt lamp etc., according to thickness by 100 ~ 2,000mJ/cm 2left and right (conversion of wavelength 365nm exposure) exposes whole face.In addition, when minus, penetrated by illumination, the auxiliary curing agent activation after making development in residual film, thus being heating and curing after can more easily carrying out.According to thickness by 100 ~ 2,000mJ/cm 2left and right (conversion of wavelength 365nm exposure) exposes whole face.
< is heating and curing (roasting) operation >
Sintering temperature when solidifying about diaphragm precursor layer, if the temperature that solidification occurs diaphragm then can be selected arbitrarily.But, then sometimes react carry out insufficient when sintering temperature is too low, and solidify deficiently.Thus, sintering temperature is preferably more than 200 DEG C, is more preferably more than 250 DEG C.In addition, the then situation, the polymer resolvent situation etc. sometimes that rise of manufacturing cost when considering excessive temperature height, is thus preferably less than 500 DEG C.Be more preferably less than 400 DEG C.In addition, roasting time is not particularly limited, but is generally more than 10 minutes, is preferably more than 20 minutes.Roasting is carried out in non-active gas or air.
< annealing operation >
Further, after formation possesses the thin-film transistor of diaphragm, the annealing of thin-film transistor is carried out.Particularly, about the element employing oxide semiconductor, because of the film based on PVD, CVD formed, the processing of the pattern of dry etching, wet etching, resist stripping process etc. and cause thin-film transistor performance that deterioration occurs, thus preferably by annealing by performance recovery.After forming the diaphragm in the present invention, by annealing more than 250 DEG C, thus by the performance recovery adding the thin-film transistor temporarily reduced man-hour.Particularly, there is following feature in the present invention: the thin-film transistor with the oxide semiconductor layer deteriorated significantly causes significantly performance recovery by annealing in the presence of oxygen.According to the degree of the deterioration of oxide semiconductor, by improving annealing temperature or extending annealing time thus the performance recovery of thin-film transistor and the reliability of element can be improved.Annealing temperature is more than 250 DEG C less than 450 DEG C, is preferably more than 300 DEG C less than 400 DEG C.Annealing time is more than 30 minutes, is preferably more than 60 minutes, but is more preferably set to more than 60 minutes less than 120 minutes from the viewpoint of cost and production efficiency.Annealing is preferably carried out in the presence of oxygen.When having the thin film transistor base plate of the diaphragm formed by organic coated film in the past, due to the annealing under such high temperature cannot be carried out, the significantly performance recovery based on annealing thus cannot be realized.But, in annealing in the presence of oxygen, consider because of the oxidation of electrode, the oxidation of diaphragm of the present invention and painted etc. the impact caused, thus preferably to carry out below 400 DEG C.In addition; the diaphragm formed by the photosensitive siloxane composition in the present invention has following advantage: owing to having photonasty; thus do not utilize dry etching etc. and to carry out pattern processing also harmless, therefore smaller to the damage of thin-film transistor performance, annealing time is short also harmless.
Embodiment
When illustrating of the present invention by each example, then as described below.
synthesis example 1 (synthesis of polysiloxanes (I))
To have mixer, thermometer, condenser pipe 2L flask in, add 25 % by weight Tetramethylammonium hydroxide (TMAH) aqueous solution 36.5g, isopropyl alcohol (IPA) 300ml, water 1.5g, in dropping funel, then prepare the mixed solution of phenyltrimethoxysila,e 44.6g, methyltrimethoxy silane 34.1g, tetramethoxy-silicane 3.8g.At 60 DEG C, this mixed solution is dripped, stir after 3 hours at the same temperature, add the 10%HCl aqueous solution and neutralize.Toluene 200ml, water 300ml is added in neutralizer, be separated into two-layer, obtained organic layer under reduced pressure concentrated and removes solvent, in concentrate, become the mode of 40 % by weight according to solid concentration and add propylene glycol methyl ether acetate (PGMEA), preparing.The molecular weight (polystyrene conversion) of the polysiloxanes (I) obtained is weight average molecular weight (Mw)=Isosorbide-5-Nitrae 20.The mode that obtained resin solution becomes 2 μm according to the thickness after prebake conditions is coated Silicon Wafer, determines the dissolution velocity to the 5%TMAH aqueous solution, result is / second.
synthesis example 2 (synthesis of polysiloxanes (II))
To have mixer, thermometer, condenser pipe 2L flask in, add 25 % by weight TMAH aqueous solution 36.5g, IPA800ml, water 2.0g, in dropping funel, then prepare the mixed solution of phenyltrimethoxysila,e 39.7g, methyltrimethoxy silane 34.1g, tetramethoxy-silicane 7.6g.At 10 DEG C, this mixed solution is dripped, stir 24 hours at the same temperature, then add the 10%HCl aqueous solution and neutralize.In neutralizer, add toluene 400ml, water 100ml, be separated into two-layer, obtained organic layer is under reduced pressure concentrated and remove solvent, and the mode becoming 40 % by weight according to solid concentration in concentrate adds PGMEA, prepares.The molecular weight (polystyrene conversion) of the polysiloxanes (II) obtained is Mw=2,200.The mode that obtained resin solution becomes 2 μm according to the thickness after prebake conditions is coated Silicon Wafer, determines the dissolution velocity to the 2.38%TMAH aqueous solution, result is / second.
positive type photo-sensitive siloxane composition A
With polysiloxanes (I): (II)=(80 % by weight): the ratio of (20 % by weight) is mixed, then polysiloxane mixture is adjusted to the PGMEA solution of 35%, with the addition of for polysiloxanes 12 % by weight 4, the diazo naphthoquinones 2.0 mole body (hereinafter referred to as " PAC ") of 4 '-(1-(4-(1-(4-hydroxyl phenol)-1-Methylethyl) phenyl) ethylidene) bis-phenol.In addition, add chemical industrial company of the SHIN-ETSU HANTOTAI KF-53 as surfactant of for polysiloxanes 0.3 % by weight, obtain photosensitive siloxane composition A.
embodiment 1 (thin film transistor base plate possessing diaphragm of the present invention)
On the Silicon Wafer that n is doped with, be provided with the silicon oxide layer of 100nm as gate insulating film.On gate insulating film, by RF sputtering method, film forming goes out amorphous state InGaZnO (70nm).After pattern forms out amorphous state InGaZnO film, pattern forms out source/drain.As source/drain material, make use of molybdenum.Thereafter, the annealing of this thin-film transistor has been carried out at 300 DEG C with 1 hour.Then, as diaphragm, utilize spin-coating method and be coated with positive type photo-sensitive siloxane composition A.After the prebake conditions of 100 DEG C, 90 seconds, define contact hole by exposing and develop.
Then, be cured under the nitrogen environment of 250 DEG C, 60 minutes and define diaphragm.The thin-film transistor possessing this diaphragm is annealed.About annealing, under oxygen atmosphere, carry out 1 hour at 250 DEG C.Diaphragm thickness is 400nm.The transmission characteristic possessing the thin-film transistor of this diaphragm after Fig. 4 illustrates annealing.Characteristic does not change substantially relative to positive voltage stress application, obtains the transmission characteristic of good thin-film transistor.
comparative example 1 (possesses the film of the diaphragm comprising emulsion and a kind of polysiloxanes transistor base)
Polysiloxanes (II) is adjusted to the PGMEA solution of 35%, with the addition of the diazo naphthoquinones 2.0 mole body (hereinafter referred to as " PAC ") of 4,4 '-(1-(4-(1-(4-the hydroxyl phenol)-1-Methylethyl) phenyl) ethylidene) bis-phenol of for polysiloxanes (II) 12 % by weight.In addition, add chemical industrial company of the SHIN-ETSU HANTOTAI KF-53 as surfactant of for polysiloxanes 0.3 % by weight, obtain photosensitive siloxane composition B.Similarly to Example 1, as diaphragm, utilize spin-coating method and be coated with photosensitive siloxane composition B.After the prebake conditions of 100 DEG C, 90 seconds, define contact hole by exposing and develop.Then, be cured under the nitrogen environment of 250 DEG C, 60 minutes, result, the contact hole formed out by developing disappears because of heat flow, cannot measure transistor characteristic.
comparative example 2 (not there is the thin film transistor base plate of diaphragm)
On grid, be provided with the silicon oxide layer of 100nm as gate insulating film.On gate insulating film, by RF sputtering method, film forming goes out amorphous state InGaZnO.After having carried out pattern formation to amorphous state InGaZnO film, pattern has formed out source/drain.As source/drain material, make use of molybdenum.Diaphragm is not set, the thin-film transistor without this diaphragm is annealed.Annealing was carried out at 300 DEG C, 2 hours.As shown in Figure 5, the performance recovery based on annealing is insufficient.Fig. 6 illustrates the transmission characteristic of thin-film transistor.Characteristic changes significantly relative to positive voltage stress application, obtains the transmission characteristic of unstable thin-film transistor.
reference example 1 (possessing the thin film transistor base plate of the diaphragm comprising a kind of polysiloxanes)
Methylphenylsilsesquioxane (methyl: phenyl=60 mole: 40 moles) has been synthesized under the existence of base catalyst.Molecular weight (polystyrene conversion) is Mw=1,800.Substantially do not dissolve relative to the 5%TMAH aqueous solution, dissolution velocity is roughly / second.Obtained polymer is adjusted to the PGMEA solution of 35%, adds chemical industrial company of the SHIN-ETSU HANTOTAI KF-53 as surfactant of for polysiloxanes 0.3 % by weight, obtain silicone composition C.On the amorphous state InGaZnO made operating similarly to Example 1, being coated with silicone composition C by spin coating after, carrying out the prebake conditions of 100 DEG C, 90 seconds, solidification (300 DEG C, 1 hour, in nitrogen), thus defining diaphragm.Utilize dry etching and define contact hole, then under oxygen atmosphere, having carried out the annealing of thin-film transistor at 300 DEG C with 1 hour.Fig. 7 illustrates the transmission characteristic of thin-film transistor.Cause having found deterioration in characteristics because of the dry etching after diaphragm coating.In addition, the characteristic close to initial stage characteristic is demonstrated by annealing.Verify the characteristic variations applied based on stress, results verification goes out characteristic variations large as shown in Figure 8.
reference example 2 (possessing the thin film transistor base plate of the diaphragm comprising acrylic material)
Prepared comprise by HEMA and the acrylic resin formed containing the polymer of the silane monomer (SHIN-ETSU HANTOTAI chemistry KBM-5103) of vinyl and, the composition of methylphenylsilsesquioxane that synthesized by reference example 1.About acrylic resin, relative to methylphenylsilsesquioxane 100 % by weight, with the addition of 30 % by weight.In the same manner as embodiment, add surfactant and prepared the solution of 35%.Operate in the same manner as reference example 1 and on amorphous state InGaZnO, form diaphragm, utilize dry etching and after defining contact hole, under oxygen atmosphere, carried out the annealing of thin-film transistor at 300 DEG C with 1 hour.Fig. 9 illustrates the transmission characteristic before and after the annealing of thin-film transistor.Even if after annealing, also there is no at the high electric current of negative voltage region in the good transistor characteristic such as flowing.
Description of reference numerals
1 thin film transistor base plate possessing diaphragm, 2 grid layers, 3 gate insulators, 4 metal oxide semiconductor layers, 5 source electrodes, 6 drain electrodes, 7 diaphragms, 8 pixel electrodes, 9 contact holes.

Claims (9)

1. a thin film transistor base plate, it is the thin film transistor base plate of the diaphragm comprising thin-film transistor and formed by the solidfied material of the photosensitive siloxane composition covering described thin-film transistor, it is characterized in that,
Described thin-film transistor has the semiconductor layer formed by oxide semiconductor,
Described photosensitive siloxane composition contains alkali dissolution velocity different at least two kinds of polysiloxanes, emulsion and solvent.
2. thin film transistor base plate according to claim 1, wherein, described polysiloxanes comprises polysiloxanes (I) and polysiloxanes (II),
This polysiloxanes (I) is that the silane compound that makes to be represented by following formula (1) under the existence of base catalyst is hydrolyzed with the silane compound represented by following formula (2) and condensation and the polysiloxanes that obtains, and the film after prebake conditions can be dissolved in 5 % by weight tetramethylammonium hydroxide aqueous solutions, and its dissolution velocity is below/second,
RSi(OR 1) 3(1)
Si(OR 1) 4(2)
In formula, R represents the aryl of the carbon number 6 ~ 20 that the straight-chain of the carbon number 1 ~ 20 that the straight-chain of carbon number 1 ~ 20, branched or cyclic alkyl or at least one methylene also can be replaced by oxygen, the aryl of branched or cyclic alkyl or carbon number 6 ~ 20 or at least one hydrogen also can replaced by fluorine, R 1represent the alkyl of carbon number 1 ~ 5,
This polysiloxanes (II) under the existence of acid or base catalyst, at least makes the silane compound of above-mentioned general formula (1) be hydrolyzed and condensation and the polysiloxanes that obtains, and the film after prebake conditions can be dissolved in 2.38 % by weight tetramethylammonium hydroxide aqueous solutions, and its dissolution velocity is more than/second.
3. thin film transistor base plate according to claim 1 and 2, wherein, described photosensitive siloxane composition is the positive type photo-sensitive siloxane composition containing different at least two kinds of polysiloxanes, diazo-naphthalene-based quinone derivative and the solvents of alkali dissolution velocity.
4. thin film transistor base plate according to claim 1 and 2, wherein, described photosensitive siloxane composition is the negative-type photosensitive silicone composition containing different at least two kinds of polysiloxanes, the auxiliary curing agent producing acid or alkali by light and the solvents of alkali dissolution velocity.
5. the thin film transistor base plate according to any one of claim 2 ~ 4, wherein, the content of the silane compound of the above-mentioned general formula (2) in described polysiloxanes (I) and polysiloxanes (II) accounts for the 3mol% to 40mol% in each polysiloxane compound.
6. the thin film transistor base plate according to any one of Claims 1 to 5, wherein, described diaphragm has the second diaphragm.
7. a manufacture method for thin film transistor base plate, it is the manufacture method of thin film transistor base plate according to claim 1, and it comprises following operation:
Prepare the operation of the photosensitive siloxane composition containing different at least two kinds of polysiloxanes, emulsion and the solvents of alkali dissolution velocity,
Described photosensitive siloxane composition is coated thin-film transistor, described solvent seasoning is formed the operation of diaphragm precursor layer,
By the operation of described diaphragm precursor layer exposure,
By the operation that the described diaphragm precursor layer exposed develops,
The described diaphragm precursor layer developed is heating and curing and forms the operation of diaphragm,
Be heating and curing possessing and the thin-film transistor of the described diaphragm the obtained operation of annealing at least one times.
8. manufacture method according to claim 7, is characterized in that, described annealing more than 250 DEG C less than 450 DEG C carry out.
9. manufacture method according to claim 7, is characterized in that, described annealing is carried out at the temperature of less than 400 DEG C under oxygen atmosphere more than 250 DEG C.
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CN110073476A (en) * 2016-11-28 2019-07-30 默克专利有限公司 The thin film transistor base plate and its manufacturing method for having protective film

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