CN101475315B - Preparation of yellow copper CIG selenide or sulfide semiconductor thin film material - Google Patents
Preparation of yellow copper CIG selenide or sulfide semiconductor thin film material Download PDFInfo
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- CN101475315B CN101475315B CN200910110998XA CN200910110998A CN101475315B CN 101475315 B CN101475315 B CN 101475315B CN 200910110998X A CN200910110998X A CN 200910110998XA CN 200910110998 A CN200910110998 A CN 200910110998A CN 101475315 B CN101475315 B CN 101475315B
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Abstract
The present invention discloses a method for preparing a chalcopyrite-type copper indium gallium selenide or sulfide semiconductor film material and relates to a semiconductor film material. The invention provides a method for preparing the chalcopyrite-type copper indium gallium selenide or sulfide semiconductor film material. A Cu metal prefabricated layer, a In metal prefabricated layer and a Ga metal prefabricated layer are deposited on a soda lime glass Mo substrate by stages through a vacuum magnetron sputtering, heating evaporation or chemical water bath electrodeposition method; N2 and H2 or Ar and H2 are mixed to obtain mixed gas; the mixed gas is introduced to a gas-solid reaction chamber; the reaction chamber is divided into two regions; a solid selenium (sulphur) sublimation region ensures that H2/N2 (or H2/Ar) gas and selenium (sulphur) steam are mixed; a hot wire catalytic gas-solid reaction region ensures that H2 and the selenium (sulphur) steam react to generate gaseous H2Se/Se(or H2S/S) mixed atmosphere; and the mixed atmosphere and the Cu metal prefabricated layer, the In metal prefabricated layer and the Ga metal prefabricated layer have thermal selenizing reaction and/or vulcanizing reaction.
Description
Technical field
The present invention relates to a kind of semiconductor film material, especially relate to a kind of selenide of chalcopyrite class copper indium gallium or the preparation method of sulfide semiconductor thin film material.
Background technology
Chalcopyrite class copper indium diselenide (CuInSe
2, be abbreviated as CIS) and serial solar cell is one of thin film solar cell most effective, the most rising in the various thin-film solar cells, its composition comprises CuInSe
2, Cu (In, Ga) Se
2, CuInS
2, CuIn (S, Se)
2, Cu (In, Ga) S
2Deng, copper-indium-galliun-selenium (Cu (In, Ga) Se
2, be abbreviated as CIGS) and represent copper indium diselenide (CIS) thin film solar cell than high open circuit voltage Voc and high-photoelectric transformation efficiency, it is different from traditional C IS hull cell.Copper-indium-galliun-selenium (CIGS) solar cell is deposit multilayer film and the photovoltaic device that constitutes respectively on common soda-lime glass or Kapton, metal sheet (aluminium, stainless steel, aluminium foil etc.) substrate, and the monomer whose battery structure is generally substrate/metal molybdenum (Mo) back electrode/light absorbing zone (CIGS)/buffer layer [CdS, ZnS, ZnSe, In (OH)
3, Zn (O, S, OH) etc.]/high resistant intrinsic i-ZnO/ conductive window layer [doping ZnO (ZnO:Al, ZnO:Ga, ZnO:B), SnO
2, ITO (tin indium oxide) etc.]/compositions such as metal gate-shaped electrode antireflective coating.Wherein the quality of the CIGS film preparation of optical absorbing layer is one of main difficulty that hinders battery industryization.The CIGS optical absorbing layer mainly forms by Cu, In, Ga and four kinds of element combinations of Se or by Cu, In, Ga, Se and five kinds of element combinations of S, is the compound [CuInSe by multiple mutual solid solution
2, CuGaSe
2, CuInS
2, CuGaS
2, Cu (In, Ga) Se
2, CuIn (S, Se)
2, Cu (In, Ga) S
2Deng] and constitute, the distribution of the stoicheiometry of each element and top and bottom element is the important factor of decision battery performance in the optical absorption thin film layer.
Produce solar cell for the industrialization big area, the preparation method of CIGS film mainly contains polynary method and the selenizing method of steaming altogether.The selenizing method is first deposited copper indium gallium on substrate (Cu-In-Ga is called for short a CIG) metal preformed layer film, and selenizing forms the CIGS film in selenium atmosphere then.Substitute selenium with sulphur equally, also can carry out the thermo-chemical treatment of sulphur (selenium behind the first sulphur) method of fractional steps behind vulcanization reaction or the first selenium, final Cu (In, Ga) S that satisfies the stoicheiometry requirement that generate
2Or Cu (In, and Ga) (Se, S)
2Compound semiconductor film.
The film of CIG film has a lot, and wherein magnetically controlled sputter method technology is easy, elemental composition is easy to control, is effectively industrialization film.Studies show that the CIGS film performance is to the composition and the structure sensitivity of CIG film, and is very big to the performance impact of follow-up CIGS film.
In the prior art, behind the metal preformed layer in selenizing or the sulfidation, both available H
2Se or H
2S gas, also available solid-state Se or S.Solid State Source selenizing or sulfuration method raw materials cost are low, basic nontoxicity, but the CIGS absorption layer lack of homogeneity that makes.
Use H
2Se or H
2S gas carries out selenizing or sulfurized principle (with H
2Se is an example) be: decomposes under 400～550 ℃ of temperature, H
2Se (g) → H
2(g)+Se
x(s) (x=1,3).The solid-state Se of Sheng Chenging wherein
xSubset and CIG film reaction generate the CIGS film.The CIGS film surface smoother that this method obtains, composition is homogeneous relatively, and grain-size is bigger, and the CIGS cell photoelectric transformation efficiency that makes is also higher.But H
2Se or H
2S all is hypertoxic gas, and inflammable, the cost height, and the requirement of transportation storage, technological operation, equipment and maintenance, vent gas treatment is very strict.In the gaseous state that in traditional gaseous state selenizing/vulcanizing oven, carries out-solid-state conversion, H
2Se/H
2The metal preformed layer that S flows through and heats with certain concentration, along with the decomposition of gaseous hydride, its dividing potential drop decreases, and selenizing or sulfuration will sharply be slowed down.Guarantee thorough selenizing or sulfuration, gaseous hydride is excessive usually, thereby causes its utilization ratio to be no more than 5% usually.So both uneconomical, also can bring serious pollution, be not suitable for extensive industrialized requirement.
Solid State Source selenizing or sulfuration method raw materials cost are low, basic nontoxicity.The shortcoming of Solid State Source selenizing or sulfuration process is: when the solid-state selenium source of (1) vacuum chamber internal heating generated saturated selenium steam, most of gaseous state selenium were with Se
5, Se
6, Se
7Exist Deng macromolecular mass or cluster form, with H
2The Se thermal degradation becomes monatomic Se and Cu, and the situation of In, the reaction of Ga atoms metal is compared, and the condition of the reaction process of macromolecular mass selenium or cluster selenium is harsher and complicated; (2) impel the back selenizing temperature of macromolecular mass selenium or cluster selenium and Cu, In, Ga atoms metal step reaction very high, almost reach the softening temperature of substrate material glass; (3) be difficult to control constant dividing potential drop atmosphere, cause the ununiformity of absorption layer.Because there is above-mentioned shortcoming in this technology, makes the CIGS absorption layer lack of homogeneity that makes, surface irregularity, thus the electricity conversion of entire cell is very low.
Solid State Source selenizing or sulfuration method that prior art adopts, the for example collaborative heating selenizing or the vulcanization process of disclosed contact thermal source of Chinese patent CN1547239A and CN1719625A and photoirradiation, the utilization ratio of solid-state selenium or sulphur is very low, and the CIGS battery efficiency of preparation is lower.Wherein, Chinese patent CN1547239A also once mentioned and used H
2With solid-state selenium (sulphur) reaction, thereby replace H
2The use of Se.But the reaction of this kind gas-solid contact generates H
2The effective content of Se is usually less than 2%, the overwhelming majority or H
2And the mixture of selenium (sulphur), it is little that actual selenizing or cure efficiency are changed improvement than Solid State Source selenium (sulphur).
Summary of the invention
The object of the present invention is to provide a kind of selenide of chalcopyrite class copper indium gallium or the preparation method of sulfide semiconductor thin film material.
Technical scheme of the present invention is to use gaseous state H
2And Se (S) mixture, by the heated filament auxiliary catalysis, reaction generates highly active H
2Se/Se (or H
2S/S) mixed atmosphere feeds traditional single chamber or continous way selenium (sulphur) and changes Reaktionsofen, finishes selenium (sulphur) and changes.
The present invention includes following steps:
1) use vacuum magnetic-control sputtering, heating evaporation or chemical bath electrodip process be substep Cu, In, the Ga metal preformed layer of sedimentation chemistry formula proportional quantity successively on soda-lime glass Mo substrate;
2) inertia is carried source gas N
2With H
2, or inertia is carried source gas Ar and H
2Mix, get mixed gas;
3) mixed gas is fed the gas-solid reaction chamber, reaction chamber is divided into two zones, and solid-state selenium (sulphur) distillation district guarantees H
2/ N
2(or H
2/ Ar) gas mixes with selenium (sulphur) steam; Heated filament catalysis gas-solid reaction district makes H
2With selenium (sulphur) vapor reaction, generate gaseous state H
2Se/Se (or H
2S/S) mixed atmosphere carries out the thermal response selenizing with Cu, In, Ga metal preformed layer again or/and vulcanize, and gets the selenide or the sulfide semiconductor thin film material of chalcopyrite class copper indium gallium.
In step 2) in, per-cent by volume, H
2Content be that inertia is carried source gas and H
226%～55% of total amount.
Silica tube or aluminum pipe can be adopted in described gas-solid reaction chamber, adopt the heater strip heating outside silica tube or aluminum pipe, and Heating temperature preferably is controlled at 210～300 ℃.Solid-state selenium (sulphur) distillation district can adopt graphite or tungsten crucible heating, and Heating temperature is preferably in 300～350 ℃.Pass to different electric currents on the heated filament, with 400～800 ℃ of control hot-wire temperatures, heated filament can adopt tungsten filament, platinum filament or Pt-Rh wire etc., and the aperture of heated filament is preferably 1.2～2.5mm.Work as H
2/ N
2(or H
2/ Ar) gas and selenium (sulphur) mixed gas can form uniform gaseous state H through heated filament
2Se/Se (or H
2S/S) mixed atmosphere.
Described selenium (sulphur) is changed reaction and can be adopted single chamber selenium (sulphur) of forvacuum to change Reaktionsofen or continous way selenium (sulphur) change Reaktionsofen, and the temperature that selenium (sulphur) is changed reaction is preferably 400～550 ℃, and the time that selenium (sulphur) is changed reaction is preferably 10～60min.
The method of the present invention's design is that inertia is carried source gas N
2Or Ar and H
2Normal temperature mixes, H
2Volume content is 26%～55%.If H
2Volume content is too low, then the H of output
2Se (H
2S) content is also low excessively, and it is not thorough to cause selenium (sulphur) to be changed; If H
2Volume content is too high, then has excessive selenium (sulphur) after selenium (sulphur) is changed reaction and is adsorbed on the CIGS surface, influences next step technology.The gas-solid reaction chamber is carried out in above-mentioned mixed gas feeding, and the reaction chamber separated into two parts is respectively solid-state selenium (sulphur) distillation district and heated filament catalysis gas-solid reaction district.
Solid-state selenium (sulphur) distillation district's effect is the steam that produces and keep selenium (sulphur).Evaporation source adopts graphite or tungsten material, and logical suitable current control evaporation source temperature is guaranteeing H
2/ N
2(or H
2/ Ar) gas and selenium (sulphur) the well-mixed while of steam, mixed gas is transported to heated filament catalysis gas-solid reaction district.
In heated filament catalysis gas-solid reaction district, the wire cloth that the aperture increases successively caudad is installed successively, material can be used tungsten, platinum, platinum rhodium etc., can adopt three road wire cloths to pass to the electric current of varying strength respectively, and the per pass net is formed successively from 800～400 ℃ thermograde.Thereby make H
2Fully react when the heated filament with selenium (sulphur) steam flow, generate gaseous state H
2Se/H
2The mixed gas of S and gaseous state Se/S.At whole gas-solid reaction chamber front end, the heated filament net of switching on together in addition, its temperature is controlled at 400～500 ℃, its objective is the H that preheating feeds
2/ N
2(or H
2/ Ar) gas causes a relatively-high temperature environment simultaneously, avoids selenium (sulphur) steam to be back to and to condense in the lower inlet region of temperature.
The metal fever silk screen in heated filament catalysis gas-solid reaction district is to H
2+ Se (S) → H
2Se (H
2S) play crucial effects.This reaction is carried out and must carried out more than 350 ℃, if but temperature is too high or high-temperature area is long, the H of generation
2Se (H
2S) can decompose again again.Therefore fast through the high temperature heated filament, can this reaction of catalysis carry out, avoided decomposing the carrying out of reversed reaction simultaneously again.In order to improve H
2Se (H
2S) productive rate, mixed gas must reduce successively through three channel temps, the heated filament net that the aperture increases successively.By the temperature of adjustment heated filament and the proportioning in silk screen aperture, can adjust H
2Se (H
2S) content in mixed atmosphere, and control H
2Se/Se (or H
2The pressure of mixed gas S/S).Heating installation can not be arranged in zone after the heated filament net, no longer decomposes to guarantee the gaseous hydride that generates.
Through above-mentioned heated filament catalytic treatment, H
2Be converted into H
2Se (H
2S) efficient can reach more than 75%.
H through heated filament catalysis generation
2Se/Se (or H
2S/S) mixed gas has very high reactive behavior, can feed traditional single chamber or continous way selenium (sulphur) changes in the vacuum reaction chamber, control 400～550 ℃ of CIG film temperatures with the mode that is rapidly heated, carry out 10～60min selenium (sulphur) and change, can finally generate the selenium or the sulfide semiconductor thin film material of copper indium gallium.
Obviously, the present invention can obtain following outstanding effect.
(1) sets up gas-solid heated filament catalytic reaction chamber, carry source gas, feasible gasification selenium/sulphur and H by inertia
2Thorough mixing, and the reaction generation contains higher H
2Se (H
2S) H of concentration
2Se/Se (or H
2S/S) mixed gas.This mixed gas has very high activity, and is convenient to adjust and keep constant gaseous state selenium/sulphur content pressure.Near the prefabricated metal thin film layer that is transported to heating, the probability and the speed of copper indium gallium metal atom and selenium in the film/sulphur generation building-up reactions increase greatly, the time that makes the metal preformed layer be transformed into the CIGS optoelectronic thin film material obviously shortens, and film quality is more even.
(2) the present invention not only combines gaseous state H
2Se (H
2S) carry out the advantage that selenium (sulphur) is changed with solid-state selenium (sulphur) source, and overcome its shortcoming separately.Comprehensive various actually operating adopt the present invention, but economical with materials consumes about 25%～30% as can be known; It is about 15% to make that the CIGS battery production time shortens, and cell conversion efficiency can improve nearly three one-tenth.Therefore, the present invention had both reduced raw material consumption, had improved selenizing/sulfuration efficient again, had also shortened the production time simultaneously, was a kind of extensive method of producing the CIGS absorption layer efficiently and safely that is fit to very much.
Description of drawings
Fig. 1 is the structural representation of the gas-solid reaction chamber that the embodiment of the invention adopted.
Fig. 2 is each regional temperature curve of the gas-solid reaction chamber that the embodiment of the invention adopted.In Fig. 2, X-coordinate is the gas-solid reaction zone, and ordinate zou is a temperature; The gas-solid reaction zone is respectively A preheating gas mixture from left to right, B selenium (sulphur) evaporation, and the C heated filament is assisted gas-solid reaction, D reaction product.
Embodiment
Following examples will the present invention is further illustrated in conjunction with the accompanying drawings.
Embodiment 1
The structural representation of the gas-solid reaction chamber that the embodiment of the invention that provides Fig. 1 adopts, wherein: 1-N
2/ Ar source of the gas, 2-H
2Source of the gas, 3-mass flowmeter MFC, 4-stainless steel ectosome, 5-gas-solid reaction chamber, 6-resistance heating wire, 7-selenium (sulphur) evaporation source, 8-tail end heated filament net, 9-front end heated filament net.
With Cu, In, the Ga metal preformed layer of vacuum magnetic-control sputtering, heating evaporation or chemical bath electrodip process substep sedimentation chemistry formula proportional quantity on soda-lime glass Mo substrate, reinstall selenizing/vulcanization reaction stove earlier.With vacuum air pump gas-solid reaction chamber and selenizing/vulcanization reaction stove are taken out in advance, reach default vacuum tightness after, close each valve.All heating systems in the connection system have specifically: (1) is according to default heating curve heating CIG metal preformed layer to 500 ℃; (2) the gas-solid reaction chamber interior walls is heated to 250 ℃; (3) front end tungsten silk screen aperture is 1.8mm, and galvanization is warming up to 400 ℃; (4) three road tungsten silk screens from front to back successively the aperture be 1.5,1.8 and 2.4mm, temperature is controlled to be 800,650,450 ℃.After treating temperature-stable, open inertia source of the gas N earlier
2And H
2Feed the gas-solid reaction chamber according to 2: 1 volume ratios, logical selenium (sulphur) the evaporation source electric current in back makes vaporization temperature at 350 ℃.Above-mentioned mixed gas directly feeds the single chamber selenizing/vulcanization reaction stove of preheating through the catalysis of three layers of heated filament net, keeps 30min after reaching 1.8 normal atmosphere, can produce the copper-indium-galliun-selenium or the sulfide semiconductor film of smoother.By the 10cm * 10cm area CIGS solar cell of this film preparation, electricity conversion can reach 15.1% after tested.
Each regional temperature distribution curve of the gas-solid reaction chamber that the embodiment of the invention adopted is referring to Fig. 2.
Claims (6)
1. the selenide of chalcopyrite class copper indium gallium or the preparation method of sulfide semiconductor thin film material is characterized in that may further comprise the steps:
1) use vacuum magnetic-control sputtering, heating evaporation or chemical bath electrodip process be substep Cu, In, the Ga metal preformed layer of sedimentation chemistry formula proportional quantity successively on soda-lime glass Mo substrate;
2) inertia is carried source gas N
2With H
2, or inertia is carried source gas Ar and H
2Mix, mixed gas, per-cent by volume, H
2Content be that inertia is carried source gas and H
226%～55% of total amount;
3) mixed gas is fed the gas-solid reaction chamber, reaction chamber is divided into two zones, and solid-state selenium or sulphur distillation district guarantee H
2/ N
2Or H
2/ Ar gas mixes with selenium or sulfur vapor; Heated filament catalysis gas-solid reaction district makes H
2With selenium or sulfur vapor reaction, generate gaseous state H
2Se/Se or H
2The mixed atmosphere of S/S, carry out thermal response selenizing or sulfuration with Cu, In, Ga metal preformed layer again, get the selenide or the sulfide semiconductor thin film material of chalcopyrite class copper indium gallium, the temperature of described heated filament is 400～800 ℃, the aperture of heated filament is 1.2～2.5mm, the temperature of selenizing or vulcanization reaction is 400～550 ℃, and the time of selenizing or vulcanization reaction is 10～60min.
2. the selenide of chalcopyrite class copper indium gallium as claimed in claim 1 or the preparation method of sulfide semiconductor thin film material is characterized in that described gas-solid reaction chamber employing silica tube or aluminum pipe, adopt the heater strip heating outside silica tube or aluminum pipe.
3. the selenide of chalcopyrite class copper indium gallium as claimed in claim 2 or the preparation method of sulfide semiconductor thin film material, the temperature that it is characterized in that described heating is 210～300 ℃.
4. the selenide of chalcopyrite class copper indium gallium as claimed in claim 1 or the preparation method of sulfide semiconductor thin film material is characterized in that described solid-state selenium or sulphur distillation district adopts graphite or tungsten crucible heating, and Heating temperature is 300～350 ℃.
5. the selenide of chalcopyrite class copper indium gallium as claimed in claim 1 or the preparation method of sulfide semiconductor thin film material is characterized in that described heated filament is tungsten filament, platinum filament or Pt-Rh wire.
6. the selenide of chalcopyrite class copper indium gallium as claimed in claim 1 or the preparation method of sulfide semiconductor thin film material, it is characterized in that described selenizing or vulcanization reaction adopt the single chamber selenizing or the vulcanization reaction stove of forvacuum, or continous way selenizing or vulcanization reaction stove.
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| CN101475315B true CN101475315B (en) | 2011-08-17 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8008198B1 (en) * | 2008-09-30 | 2011-08-30 | Stion Corporation | Large scale method and furnace system for selenization of thin film photovoltaic materials |
| CN101789469B (en) * | 2010-03-05 | 2013-01-02 | 中国科学院上海硅酸盐研究所 | Method for preparing light absorption layer of Cu-In-Ga-Se-S thin film solar cell |
| CN102394256B (en) * | 2011-11-16 | 2013-09-11 | 浙江大学 | Preparing method of copper-indium-sulfide array film used for solar cell absorbed layer |
| TW201322472A (en) * | 2011-11-21 | 2013-06-01 | Axuntek Solar Energy | Rapid thermal processing system and sulphidation method thereof |
| CN103572089B (en) * | 2013-11-12 | 2015-10-28 | 中国科学院金属研究所 | A kind of preparation method of Cu-Im-Ga-Se quaternary semiconductor alloy |
| CN105551933A (en) * | 2015-12-08 | 2016-05-04 | 中国电子科技集团公司第十八研究所 | Selenium source fragmentation rectifying device for manufacturing CIGS battery |
| CN105932093B (en) * | 2016-04-26 | 2018-06-19 | 河南大学 | A kind of preparation method of high quality CIGS thin film solar battery obsorbing layer |
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