CN102709351A

CN102709351A - Cuprous sulfide film with preferred orientation growth

Info

Publication number: CN102709351A
Application number: CN201210181358XA
Authority: CN
Inventors: 刘科高; 孙昌; 李静; 许斌; 石磊
Original assignee: Shandong Jianzhu University
Current assignee: Shandong Jianzhu University
Priority date: 2012-06-05
Filing date: 2012-06-05
Publication date: 2012-10-03

Abstract

The invention provides a cuprous sulfide film with preferred orientation growth and belongs to the technical field of semiconductor films. The cuprous sulfide film is obtained through the following steps of firstly cleaning a glass substrate; then putting CuCl2.2H2O into a solvent, spincoating the mixture on the glass substrate to obtain a precursor film, drying the precursor film, putting the dried precursor film into a sealable container containing sulfur powder and hydrazine hydrate and ensuring that the precursor film sample is not contacted with the hydrazine hydrate and the sulfur powder; and finally drying the precursor film. The obtained cuprous sulfide film is subjected to crystal growth along a preferred orientation [111] and is better in continuity and uniformity.

Description

A kind of sulfuration two bronze medal films of preferred orientation growth

Technical field

The invention belongs to the semiconductor film technique field, relate in particular to a kind of sulfuration two bronze medal films of preferred orientation growth.

Background technology

Along with society and expanding economy; China's total energy consumption increases severely; The pollution that the energy scarcity and the consumption energy bring has become the outstanding problem in the domestic social development, and therefore developing clean energy resource all has important meaning to protecting environment, sustainable economic development and constructing harmonious society.In order to utilize the renewable resource of this cleaning of solar energy, safety and environmental protection more fully, the research and development that is used for the photoelectric material of solar cell in recent years comes into one's own day by day.

Transient metal sulfide is widely used owing to it has excellent photoelectric performance, and wherein the sulfide of copper is a kind of important transient metal sulfide.The compound that Cu and S form is because they in the polytropy of forming aspects such as metering ratio, crystal morphology, structure, valence state, cause these compounds that some special photoelectric properties are arranged, and this has caused that people greatly pay close attention to.As a kind of important semi-conducting material, the sulfide of copper is widely used in aspects such as solar cell, filter, nanotube switch, thermoelectricity or optical-electrical converter, conductive electrode, superconductor, vessel transducer.Since finding Cu _xSince the S/CdS heterostructure has the photovoltaic special efficacy to answer, Cu _xS receives people's attention as a kind of important photoelectric semiconductor material.As P type semiconductor, Cu ₂S, Cu _1.8The energy gap of S and CuS is respectively 1.2,1.5 and 2.0eV.Because its complicated structure and valence state and adjustable energy gap, be desirable cheapness, solar cell material efficiently.

The preparation method of the sulfide film of copper mainly contains electrochemical method, the absorption of continuous ionic layer and reaction, ald (ALD), microwave-assisted chemical bath deposition, chemical vapor reaction, the meteoropathic reaction of plasma sputter layer, chemical bath deposition at present.Because the cost of material of copper sulfide film is low, be a kind of very rising optoelectronic thin film material therefore.Control sulfide semiconductor growth for Thin Film orientation is the important channel of its performance of regulation and control, so the sulfide film of preferred orientation growth is one of focus of research.Document (Liu KG, Liu H, Wang JY, et al, Synthesis and characterization of Cu have been published ₂Seprepared by hydrothermal co-reduction.Journal of Alloys and Compounds.Vol.484; No.1-2; SEP182009:674-676) prepared the Cu2Se dusty material in; Though with the method that obtains material in the present patent application similarity is arranged, the former is a powder, and composition is different.And gained is a thin-film material in the present patent application, and these will be different at formation and crystal growing process and mechanism with dusty material, and dusty material is difficult to obtain the material of same crystal orientation preferential growth.

As method noted earlier, other method does not prepare the sulfuration two bronze medal films of preferred orientation yet.Relevant with the present invention also have following document:

[1]A.Bollero，M.Grossberg，B.Asenjo，M.T.Gutiérrez，CuS-based?thin?films?for?architectural?glazingapplications?produced?by?co-evaporation：Morphology，optical?and?electrical?properties，Surface&CoatingsTechnology?204(2009)593-600.

Mainly describe common steaming legal system and be equipped with glass of building CuS film and pattern and photoelectric properties.

[2]Mudi?Xin，KunWei?Li，Hao?Wang，Synthesis?of?CuS?thin?films?by?microwave?assisted?chemical?bathdeposition，Applied?Surface?Science?256(2009)1436-1442.

Mainly describe meagre assistant chemical and bathed the synthetic CuS film of sedimentation.

[3]Y.Rodríguez-Lazcano，H.Martínez，M.Calixto-Rodríguez，A. Rodríguez，Properties?of?CuS?thin?filmstreated?in?air?plasma，Thin?Solid?Films?517(2009)5951-5955.

Mainly describe chemical deposition CuS film, and in air plasma, carried out reprocessing.

[4]M.Ali?Yil?dirim，Aytunc?Ates，Aykut?Astam，Annealing?and?light?effect?on?structural，optical?and?electricalproperties?of?CuS，CuZnS?and?ZnS?thin?films?grown?by?the?SILAR?method，Physica?E?41(2009)1365-1372.

Mainly described to absorb with reaction method and prepare CuS, CuZnS, ZnS film, and annealing and light are to the influence of membrane structure and photoelectric properties with the continuous ionic layer.

[5]Jun?Liu，Dongfeng?Xue，Solvothermal synthesis?of?copper?sulfide?semiconductor?micro/nanostructures，Materials?Research?Bulletin?45(2010)309-313.

The synthetic micron of the hot method of solution, nano level copper sulfide semiconductor have mainly been described.

[6]Fuwei?Zhuge，Xiaomin?Li，Xiangdong?Gao，Xiaoyan?Gan，Fengling?Zhou，Synthesis?of?stable?amorphousCu ₂S?thin?film?by?successive?ion?layer?adsorption?and?reaction?method，Materials?Letters?63(2009)652-654.

Mainly described with the continuous sheath absorption and the Cu of the amorphous state of the method synthesizing stable of reaction ₂The S film.

[7]Yung-Tang?Nien，In-Gann?Chen，Rapid?thermal?annealing?of?chemical?bath-deposited?Cu _xS?films?and?theirCharacterization，Journal?of?Alloys?and?Compounds?471(2009)553-556.

Mainly describe chemical bath deposition method and prepared Cu _xThe S film, and the characteristic of film and rapid thermal treatment are to the influence of film.

[8]S.V.Bagul，S.D.Chavhan，Ramphal?Sharmab，Growth?and?characterization?of?Cu _xS(x＝1.0，1.76，and?2.0)thinfilms?grown?by?solution?growth?technique(SGT)，Journal?of?Physics?and?Chemistry?of?Solids?68(2007)1623-1629.

Mainly describe solution growth method and prepared Cu _xS (x=1.0,1.76,2.0) film, and studied growth for Thin Film and characteristic.

Summary of the invention

The present invention is in order to solve the deficiency of prior art, and invented a kind of sulfuration two bronze medal films of preferred orientation growth.

The present invention adopts spin-coating method to prepare precursor thin-film, reduces synchronously and vulcanize to prepare the sulfuration two bronze medal films that preferred orientation is grown, and the employing soda-lime glass is a substrate, with CuCl ₂2H ₂O and S powder are raw material; Two or more mixture with deionized water, ethylene glycol, monoethanolamine, these four kinds of raw materials of ammoniacal liquor is a solvent; With ammoniacal liquor, hydrochloric acid is the pH value that assist medium is adjusted solution, prepares the certain thickness precursor thin-film that contains copper compound with spin-coating method earlier, is reducing agent with the hydrazine hydrate; Heating at a lower temperature in closed container makes the precursor thin-film reduction and obtains target product with S element generation synthetic reaction simultaneously.

The present invention is obtained by the step of following order:

A. carrying out the cleaning of glass substrate, is that 2mm * 2mm sheet glass is put into chloroform by volume with size: the solution of ethanol=5: 1, ultrasonic waves for cleaning 30min; Again sheet glass is put into acetone: the solution of distilled water=5: 1, ultrasonic waves for cleaning 30min; In distilled water, glass substrate is used sonic oscillation 30min again; The above-mentioned glass substrate that obtains is emitted on sends in the glass dish in the baking oven, 100 ℃ down oven dry supply the system film to use.

B. with CuCl ₂2H ₂O puts into solvent, fully dissolving, and regulate the pH value.Specifically, can be with 4.0～6.0 parts of CuCl ₂2H ₂O puts into 30～150 parts solvent, and solution is mixed, and can add the pH value that ammoniacal liquor, hydrochloric acid assistant are adjusted solution, and wherein solvent is at least two kinds a mixed solution in deionized water, ethylene glycol, monoethanolamine, the ammoniacal liquor.

C. make the outside evenly substrate of the said solution of smearing step b, and oven dry, the precursor thin-film sample obtained.Can above-mentioned solution be dripped on the glass substrate that is placed on the sol evenning machine; Restart sol evenning machine with 200～3500 rev/mins of rotation certain hours; After making solution on dripping be coated with evenly, 100 ℃ substrate dried after, repeat once more to drip and dry again after going up aforementioned solution and rotary coating; So repeat 5～15 times, so on glass substrate, obtained certain thickness precursor thin-film sample.

D. step c gained precursor thin-film sample is placed on the support, but put into the closed container of sulphur powder, hydrazine hydrate, the precursor thin-film sample is not contacted with sulphur powder, hydrazine.The hydrazine hydrate of putting into is 30.0～40.0 parts, sulphur powder 1.0～2.5.

E. the above-mentioned closed container that the precursor thin-film sample is housed is put into baking oven, is heated between 160～220 ℃, temperature retention time 10～20 hours, cool to room temperature takes out then, make its air dry after, promptly obtain the sulfuration two bronze medal films of preferred orientation growth.

The present invention does not need the high temperature high vacuum condition, and low to the instrument and equipment requirement, production cost is low, and production efficiency is high, easy operating.Gained vulcanizes two bronze medal films has continuity and uniformity preferably; Characteristics with preferred orientation growth along [111] crystal orientation; The sulfuration two bronze medal films of this oriented growth can be significantly different with other direction along the performance in [111] crystal orientation, can be used for making the thin film solar cell device.

Description of drawings

Accompanying drawing 1 is the XRD figure spectrum that gained vulcanizes two bronze medal films behind 180 ℃ of following reaction 10h.Compare with the standard spectrum of sulfuration two bronze medals, analysis can know that gained vulcanizes two bronze medal films and has single diffraction maximum, along the growth of (111) crystal face, has preferred orientation [111] crystal orientation.

Embodiment

Embodiment 1

A. the cleaning of glass substrate: (size is 2mm * 2mm) to carry out the glass cleaning substrate as previously mentioned.

B. with 5.316 parts of CuCl ₂2H ₂O puts into vial, adds 75.614 parts of monoethanolamines, 113.421 parts of deionized waters, add ammoniacal liquor to PH be 8.0, utilize more than the ultrasonic vibration 30min, the material in the solution is evenly mixed.

C. above-mentioned solution is dripped on the glass substrate that is placed on the sol evenning machine, restart sol evenning machine, sol evenning machine rotated 5 seconds with 200 rev/mins; With 3000 rev/mins of rotations 15 seconds; After making solution on dripping be coated with evenly, 100 ℃ substrate dried after, repeat once more to drip and dry again after going up aforementioned solution and rotary coating; So repeat 10 times, so on glass substrate, obtained certain thickness precursor thin-film sample.

D. the precursor thin-film sample of above-mentioned technology gained is put into sealable container, and put into 1.980 parts of sulphur powder and 37.807 parts of hydrazine hydrates, the precursor thin-film sample places it is not contacted with sulphur powder, hydrazine.

E. the above-mentioned closed container that the precursor thin-film sample is housed is put into baking oven; Be heated between 180 ℃; Temperature retention time 10 hours, cool to room temperature takes out then, make its air dry after; Promptly obtain the sulfuration two bronze medal films of preferred orientation growth, the X-ray diffractogram of its phase composition analysis and crystallization direction is as shown in Figure 1.

Claims

1. the sulfuration two bronze medal films of preferred orientation growth is characterized by the growth along [111] crystal orientation, are obtained by the step of following order:

A. the cleaning of glass substrate;

B. with CuCl ₂2H ₂O puts into 30～200 parts solvent, and the material in the solution is fully dissolved;

C. make the outside evenly substrate of the said solution of smearing step b, and oven dry, the precursor thin-film sample obtained;

D. step c gained precursor thin-film sample is placed on the support, put into sulphur (S) but the closed container of powder, hydrazine hydrate, the precursor thin-film sample is not contacted with hydrazine, sulphur powder;

E. with the steps d gains, carry out drying, obtain the sulfuration two bronze medal films of preferred orientation growth along [111] crystal orientation.