CN102153288A - Method for preparing copper disulfide thin film with preferred orientation - Google Patents
Method for preparing copper disulfide thin film with preferred orientation Download PDFInfo
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- CN102153288A CN102153288A CN 201010569122 CN201010569122A CN102153288A CN 102153288 A CN102153288 A CN 102153288A CN 201010569122 CN201010569122 CN 201010569122 CN 201010569122 A CN201010569122 A CN 201010569122A CN 102153288 A CN102153288 A CN 102153288A
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- thin film
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- films
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Abstract
The invention relates to a method for preparing a copper disulfide thin film with preferred orientation and belongs to the technical field of preparation of a semiconductor thin film. The copper disulfide thin film with the preferred orientation is prepared by the following steps of: firstly cleaning a glass substrate; then placing CuCl2 2H2O into a solvent and regulating a pH value; obtaining a precursor thin film on the glass substrate by a spin coating method; drying the precursor thin film; placing the dried precursor thin film into a sealable container with powdered sulfur and hydrazine hydrate so that a precursor thin film sample is not contacted with hydrazine and the powdered sulfur; and finally drying to obtain the copper disulfide thin film with the preferred orientation. The method is carried out without the conditions of the high temperature and high vacuum, has low requirements on instrument equipment, has low production cost and high production efficiency and is easy to operate. The obtained copper disulfide thin film with the preferred orientation has high continuity and uniformity. The invention provides the production method for preparing the copper disulfide thin film with the preferred orientation, which has low cost and capability of realizing industrialization.
Description
Technical field
The invention belongs to the semiconductor film preparing technical field, relate in particular to a kind of preparation and select the preparation method that outstanding orientation is vulcanized two bronze medal films.
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 all has important meaning to protecting environment, sustainable economic development and constructing harmonious society.In order to utilize the renewable resources of this cleaning of sun power, 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 semiconductor material, the sulfide of copper is widely used in aspects such as solar cell, spectral filter, nanotube switch, thermoelectricity or photoelectric commutator, conductive electrode, superconductor, vessel transmitter.Since finding Cu
xSince the S/CdS heterojunction structure has the photovoltaic special efficacy to answer, Cu
xS is subject to 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 ideal 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 raw materials cost of cupric sulfide film is low, is a kind of very rising optoelectronic thin film material therefore, but has operational path complexity, preparation cost height now, thereby need explore preparation technology cheaply equally.
As method noted earlier, other method also has different defectives.Related to 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?thinfilms?treated?in?air?plasma，Thin?Solid?Films?517(2009)5951-5955.
Mainly describe electroless plating CuS film, and in air plasma, carried out aftertreatment.
[4]M.Ali?Yildirim，Aytunc?Ates，Aykut?Astam，Annealing?and?light?effect?on?structural，optical?and?electricalproperties?ofCuS，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?amorphous?Cu
2Sthin?film?by?successive?ion?layer?adsorption?and?reaction?method，Materials?Letters?63(2009)652-654.
Mainly described with the Cu of successive sheath absorption with 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?CuxS?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 feature of film and rapid thermal process 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 deficiencies in the prior art, and a kind of and preparation method prior art are diverse to select the preparation technology that outstanding orientation is vulcanized two bronze medal films and invented.
The present invention adopts spin-coating method to prepare precursor thin-film, reduces synchronously and vulcanize to prepare sulfuration two copper film materials, and the employing soda-lime glass is a substrate, with CuCl
22H
2O, the S powder is a raw material, two or more mixture with deionized water, ethylene glycol, thanomin, 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, earlier prepare the certain thickness precursor thin-film that contains copper compound with spin-coating method, with the hydrazine hydrate is reductive agent, and heating at a lower temperature in encloses container makes the precursor thin-film reduction and obtains target product with S element generation building-up reactions simultaneously.
Concrete preparation method of the present invention comprises the step of following order:
A. carrying out the cleaning of glass substrate, is that 2mm * 2mm sheet glass is put into trichloromethane by volume with size: the solution of ethanol=5: 1, ultrasonic cleaning 30min; Again sheet glass is put into acetone: the solution of distilled water=5: 1, ultrasonic cleaning 30min; In distilled water, glass substrate 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 use for the system film.
B. with CuCl
22H
2O puts into solvent, fully dissolving, and regulate 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 auxiliary are adjusted solution, and wherein solvent is at least two kinds a mixing solutions in deionized water, ethylene glycol, thanomin, the ammoniacal liquor.
C. make the outside evenly substrate of the described solution of smearing step b, and oven dry, the precursor thin-film sample obtained.Above-mentioned solution can 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, dry again after repeating to drip last aforementioned solution and rotary coating once more, 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 encloses 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 encloses container that the precursor thin-film sample is housed is put into baking oven, is heated between 160～220 ℃, soaking time 10～20 hours, cool to room temperature takes out then, make its seasoning after, promptly obtain selecting the sulfuration two bronze medal films of outstanding orientation.
The present invention does not need the high temperature high vacuum condition, and low to the plant and instrument requirement, production cost is low, production efficiency height, easy handling.Gained vulcanizes two bronze medal films continuity and homogeneity preferably, characteristics with oriented growth, the crystalline orientation of the easy controlled target product of this novel process, for prepare high performance sulfuration two bronze medal films provide a kind of cost low, can realize large-scale industrial production.
Description of drawings
Accompanying drawing 1 is the XRD figure spectrum that gained vulcanizes two bronze medal films behind 180 ℃ of following reaction 10h.With the standard spectrum of sulfuration two bronze medals relatively, analyze as can be known gained and vulcanize two bronze medal films and have single diffraction peak, along the growth of (111) crystal face, have and select outstanding orientation [111] crystal orientation.
Embodiment
Embodiment 1
A. the cleaning of glass substrate: (size is 2mm * 2mm) to clean glass substrate as previously mentioned.
B. with 5.316 parts of CuCl
22H
2O puts into vial, adds 75.614 parts of thanomins, 113.421 parts of deionized waters, add ammoniacal liquor to PH be 8.0, utilize more than the ultrasonic vibration 30min, make the material uniform mixing in the solution.
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 go up oven dry again after aforementioned solution and the 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 encloses container that the precursor thin-film sample is housed is put into baking oven, be heated between 180 ℃, soaking time 10 hours, cool to room temperature takes out then, after making its seasoning, promptly obtain the sulfuration two bronze medal films of preferred orientation, the X-ray diffractogram of its phase composite analysis and crystallization direction as shown in Figure 1.
Embodiment 2
A. the cleaning of glass substrate: (size is 2mm * 2mm) to clean glass substrate as previously mentioned.
B. with 5.316 parts of CuCl
22H
2O puts into 113.421 parts of ethylene glycol, 75.614 parts the mixing solutions of ammoniacal liquor, add hydrochloric acid to PH be 3.5, utilize more than the ultrasonic vibration 30min, make the material uniform mixing in the solution.
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 go up oven dry again after aforementioned solution and the 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 encloses container that the precursor thin-film sample is housed is put into baking oven, is heated between 180 ℃, soaking time 12 hours, cool to room temperature takes out then, make its seasoning after, promptly obtain selecting the sulfuration two bronze medal films of outstanding orientation.
Claims (7)
1. select the preparation method that outstanding orientation is vulcanized two bronze medal films for one kind, comprise 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, and adjusts pH value to 3～10;
C. make the outside evenly substrate of the described 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 encloses 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 selecting the sulfuration two bronze medal films of outstanding orientation.
2. as claimed in claim 1ly select the preparation method that outstanding orientation is vulcanized two bronze medal films, it is characterized in that the described washing of step a is that the glass substrate size is 2mm * 2mm, puts into trichloromethane by volume: the solution of ethanol=5: 1, ultrasonic cleaning; Again sheet glass is put into acetone: the solution of distilled water=5: 1, ultrasonic cleaning; Again in distilled water with the glass substrate sonic oscillation; The above-mentioned glass substrate that obtains is emitted on sends in the baking oven oven dry in the glass dish and use for the system film.
3. the preparation method who selects the sulfuration two bronze medal films of outstanding orientation as claimed in claim 1 is characterized in that the described CuCl of step b, d
22H
21.0～2.5 parts in O4.0～6.0 part, S powder.
4. the preparation method who selects the sulfuration two bronze medal films of outstanding orientation as claimed in claim 1 is characterized in that the described solvent of step b is at least a in deionized water, ethylene glycol, thanomin, ammoniacal liquor, the hydrochloric acid.
5. the preparation method who selects outstanding orientation cupric sulfide two films as claimed in claim 1, it is characterized in that, the described substrate of evenly smearing of step c, be to smear by sol evenning machine, sol evenning machine is with 200～3500 rev/mins of rotations, after then substrate being dried, so repeat once more 5～15 times, obtained certain thickness precursor thin-film sample.
6. the preparation method who selects the sulfuration two bronze medal films of outstanding orientation as claimed in claim 1 is characterized in that, puts into 35.0～40.0 parts of hydrazine hydrates in the described encloses container of steps d.
7. as claimed in claim 1ly select the preparation method that outstanding orientation is vulcanized two bronze medal films, it is characterized in that the described drying of step e is heated between 160～220 ℃ for putting into baking oven, soaking time 10～20 hours, cool to room temperature takes out then.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602961A (en) * | 2012-03-12 | 2012-07-25 | 山东建筑大学 | Method for preparing preferentially oriented ammonium chloride thin film |
| CN102709351A (en) * | 2012-06-05 | 2012-10-03 | 山东建筑大学 | Cuprous sulfide film with preferred orientation growth |
| CN102863155A (en) * | 2012-09-25 | 2013-01-09 | 宁波大学 | Preparation method of solar thermal shield glass |
| CN103449734A (en) * | 2013-07-09 | 2013-12-18 | 山东建筑大学 | Method for preparing copper-aluminum-sulfur film |
| CN103938189A (en) * | 2014-04-30 | 2014-07-23 | 齐鲁工业大学 | Method for quickly and efficiently preparing copper sulphide nano film |
| CN105428458A (en) * | 2015-12-17 | 2016-03-23 | 山东建筑大学 | Method for preparing copper-indium sulfide optoelectronic thin film by adopting sulfate system two-step method |
| CN105428459A (en) * | 2015-12-17 | 2016-03-23 | 山东建筑大学 | Method of preparing CuInS2 photoelectric thin film by acetate system two-step method |
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| CN1949546A (en) * | 2006-11-10 | 2007-04-18 | 中国科学院上海硅酸盐研究所 | Method for preparing p type copper sulfide transparent conducting film |
| CN101638777A (en) * | 2009-07-20 | 2010-02-03 | 北京工业大学 | Method for depositing copper sulphide nano film rapidly in low temperature |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1949546A (en) * | 2006-11-10 | 2007-04-18 | 中国科学院上海硅酸盐研究所 | Method for preparing p type copper sulfide transparent conducting film |
| CN101638777A (en) * | 2009-07-20 | 2010-02-03 | 北京工业大学 | Method for depositing copper sulphide nano film rapidly in low temperature |
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| 《Journal of Alloys and Compounds》 20090511 Kegao Liu et. al. Synthesis and characterization of Cu2Se prepared by hydrothermal co-reduction 674-676 1-7 , 第484期 * |
| 《功能材料与器件学报》 20080229 王群等 以CuCl纳米棒薄膜为前驱体制备CuS纳米/微米管和CuO纳米/微米晶薄膜 1-4 1-7 第14卷, 第1期 * |
| 《润滑与密封》 20070228 张翼东等 CuS2PAA2APS有机无机复合膜的制备及其摩擦学行为研究 85-87 1-7 第32卷, 第2期 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602961A (en) * | 2012-03-12 | 2012-07-25 | 山东建筑大学 | Method for preparing preferentially oriented ammonium chloride thin film |
| CN102709351A (en) * | 2012-06-05 | 2012-10-03 | 山东建筑大学 | Cuprous sulfide film with preferred orientation growth |
| CN102863155A (en) * | 2012-09-25 | 2013-01-09 | 宁波大学 | Preparation method of solar thermal shield glass |
| CN103449734A (en) * | 2013-07-09 | 2013-12-18 | 山东建筑大学 | Method for preparing copper-aluminum-sulfur film |
| CN103449734B (en) * | 2013-07-09 | 2015-12-02 | 山东建筑大学 | A kind of method preparing copper aluminium sulphur optoelectronic film |
| CN103938189A (en) * | 2014-04-30 | 2014-07-23 | 齐鲁工业大学 | Method for quickly and efficiently preparing copper sulphide nano film |
| CN105428458A (en) * | 2015-12-17 | 2016-03-23 | 山东建筑大学 | Method for preparing copper-indium sulfide optoelectronic thin film by adopting sulfate system two-step method |
| CN105428459A (en) * | 2015-12-17 | 2016-03-23 | 山东建筑大学 | Method of preparing CuInS2 photoelectric thin film by acetate system two-step method |
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Application publication date: 20110817 |