CN101840957A - Preparation method for anti-vacuum manufacture of copper-indium-gallium-selenium slurry - Google Patents

Preparation method for anti-vacuum manufacture of copper-indium-gallium-selenium slurry Download PDF

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Publication number
CN101840957A
CN101840957A CN201010111478A CN201010111478A CN101840957A CN 101840957 A CN101840957 A CN 101840957A CN 201010111478 A CN201010111478 A CN 201010111478A CN 201010111478 A CN201010111478 A CN 201010111478A CN 101840957 A CN101840957 A CN 101840957A
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China
Prior art keywords
selenium
indium gallium
copper indium
copper
gallium selenide
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CN201010111478A
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Chinese (zh)
Inventor
林群福
陈文仁
杨益郎
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昆山正富机械工业有限公司
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Priority to CN201010111478A priority Critical patent/CN101840957A/en
Publication of CN101840957A publication Critical patent/CN101840957A/en

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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/52Manufacturing of products or systems for producing renewable energy
    • Y02P70/521Photovoltaic generators

Abstract

The invention relates to a preparation method for the anti-vacuum manufacture of copper-indium-gallium-selenium slurry, which mainly uses a binary or ternary selenide flaky material containing IB and IIIA families when copper-indium-gallium-selenium or copper-indium-gallium-selenium (sulfur) slurry is prepared. The method comprises the steps of: mixing no more than 50% of flaky material with a solvent or a relevant additive and stirring evenly so as to prepare the slurry containing copper, indium, gallium and selenium or copper, indium, gallium and selenium (sulfur); and adding VIA family powder in a rapid thermal annealing (RTA) process and volatilizing the powder at high temperature for supplementing the loss of the volatilization of the sulfur or the selenium of a copper-indium-gallium-selenium or copper-indium-gallium-selenium (sulfur) precursor layer at high temperature. Because the invention does not use a high-temperature reduction method and a selenization method, the invention saves the equipment cost and avoids the use of dangerous hydrogen selenide. Meanwhile, because of using particles with different shapes, the invention enhances the compactness of a generated film.

Description

The concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent

Technical field

The present invention relates to a kind of concocting method of copper indium gallium selenide sizing agent slurry, particularly relate to a kind of concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent.

Background technology

In recent years, the new line of and environmental consciousness surging along with international oil price, green energy resource has become the main flow of new forms of energy, wherein solar cell is again because of being the stable radiant energy of taking from the sun, the source can be inexhausted, and therefore more various countries pay attention to draw from one to make good the deficits of another invariably a large amount of development costs and subsidies granted for policy considerations, to foster local solar cell industry, make that the development of global solar industry is very quick.

First generation solar energy module comprises the solar energy module of monocrystalline silicon and polysilicon, though photoelectric conversion efficiency height and volume production technology maturation, because the material cost height, and Silicon Wafer influences follow-up volume production scale often because of the demand source of goods deficiency of semi-conductor industry.Therefore, comprise (CIGSS) thin-film solar module of the second generation of film and Cadimium telluride thin film of amorphous silicon membrane, Copper Indium Gallium Selenide (CIGS) film or Copper Indium Gallium Selenide (sulphur), in development and ripe gradually in recent years, wherein, therefore come into one's own especially again with the conversion efficiency of Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) solar cell the highest (element cell can up to 20% module about 14%).

Seeing also shown in Figure 1ly, is the Copper Indium Gallium Selenide of existing located by prior art or the schematic diagram of Copper Indium Gallium Selenide (sulphur) solar battery structure.As shown in Figure 1; the copper indium gallium selenium solar cell structure of existing located by prior art comprises substrate 10; first conductive layer 20; Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) absorbed layer 30; resilient coating 40; the insulating barrier 50 and second conductive layer 60; wherein substrate 10 can be glass plate; aluminium sheet; Stainless Steel plate or plastic plate; first conductive layer 20 generally comprises metal molybdenum; be used as backplate; Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) absorbed layer 30 comprises the copper of proper proportion; indium; gallium and selenium; be used as p type film; be main light absorbed layer; resilient coating 40 can comprise cadmium sulfide (CdS); be used as n type film; insulating barrier 50 comprises zinc oxide (ZnO); in order to protection to be provided, second conductive layer 60 comprises zinc oxide aluminum (ZnO:Al), in order to connect front electrode.

The manufacture method of above-mentioned Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) solar cell mainly is divided into vacuum technology and adopting non-vacuum process according to the manufacturing environment of Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) absorbed layer.Vacuum technology comprises sputtering method or vapour deposition method, and shortcoming is that cost of investment is higher and stock utilization is lower, so the integral manufacturing cost is higher.Adopting non-vacuum process comprises print process or electrodeposition process, and shortcoming is that technology is still immature, does not still have the larger area commercial prod.But adopting non-vacuum process still has the advantage that manufacturing equipment is simple and process conditions is reached easily, thereby has suitable business potential.

The adopting non-vacuum process of Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) absorbed layer is to allocate Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) slurry or ink (Ink) earlier, in order to be applied on the molybdenum layer.

Existing located by prior art Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) slurry preparation are to mix to contain with proper proportion earlier to mix IB, the oxide of IIIA and VIA family element is to form the original oxide powder that contains Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) mixing, add the solvent of proper proportion again, and stir to form original Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) slurry, add solid (binder) or interfacial agent then property at last, and mix to form last Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) slurry with raising Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) absorbed layer and molybdenum backplate.

The shortcoming of above-mentioned existing located by prior art is, when desire is removed the oxygen in the oxide, need under excessive temperature, to use this oxide of hydrogen reducing, need use hydrogen selenide to carry out the selenizing process simultaneously, not only can improve equipment cost, and hydrogen selenide toxicity is very strong, if careless the use has deadly danger, simultaneously if in the reduction process, still have oxygen molecule to remain in last Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) absorbed layer, can influence the optical absorption characteristics of Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) absorbed layer, even influence efficient.Therefore, need a kind of technology that does not need high temperature reduction and selenizing etc., uses cheap and simple equipment can deposit method with the light absorbing zone of manufacturing Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) solar cell.

Simultaneously because general nano metal or the metal compound powders that uses all is to use spherical particle, these spherical particles easily produce the space when piling up, therefore need a kind of particle that contains the difformity material to plug the gap, make pile up tightr, to improve the compactness of film.

This shows that the concocting method of above-mentioned existing anti-vacuum manufacture copper indium gallium selenide sizing agent obviously still has inconvenience and defective, and demands urgently further being improved in method and use.In order to solve the problem of above-mentioned existence, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but do not see always that for a long time suitable design finished by development, and conventional method does not have appropriate method to address the above problem, this obviously is the problem that the anxious desire of relevant dealer solves.Therefore how to found a kind of concocting method of new anti-vacuum manufacture copper indium gallium selenide sizing agent, real one of the current important research and development problem that belongs to, also becoming the current industry utmost point needs improved target.

Summary of the invention

The objective of the invention is to, overcome the defective of the concocting method existence of existing anti-vacuum manufacture copper indium gallium selenide sizing agent, and provide a kind of concocting method of new anti-vacuum manufacture copper indium gallium selenide sizing agent, technical problem to be solved is to make it when allotment Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) slurry, use contains IB, the binary of IIIA family or ternary selenides sheeting, wherein to be no more than 50% lamellar material, solvent or the associated additives of arranging in pairs or groups again stirs, to be made into the slurry that contains Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur), and at short annealing heat treatment (Rapid thermal annealing, RTA) add VIA family powder in the process, this powder is at high temperature volatilized, the sulphur under additional Copper Indium Gallium Selenide of help or Copper Indium Gallium Selenide (sulphur) the precursor layer high temperature or the loss of selenium volatilization are very suitable for practicality.

The object of the invention to solve the technical problems realizes by the following technical solutions.The concocting method of a kind of anti-vacuum manufacture copper indium gallium selenide sizing agent that proposes according to the present invention, in order under non-vacuum environment, to make a copper indium gallium selenide sizing agent, this copper indium gallium selenide sizing agent is in order to be coated on the molybdenum layer and form an absorbed layer, this method may further comprise the steps: at first, according to a formula rate, mix chip shape and contain the binary or the ternary selenide material of IB, IIIA family element, to form an original mixed powder, and this IB family element comprises copper, and this IIIA family element comprises indium or gallium or indium gallium composite material; Then, add solvent as mixed media; And last, interpolation interfacial agent or solid also stirs to finish the allotment of slurry, uses to form the copper indium gallium selenide sizing agent that contains IB, IIIA family and selenium element.

The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.

The concocting method of aforesaid anti-vacuum manufacture copper indium gallium selenide sizing agent, the formula rate of wherein said original mixed powder are that the not ear ratio that comprises this IB, IIIA family element and selenium element equals 0.9-1.0: 1.0: 2.0.

The concocting method of aforesaid anti-vacuum manufacture copper indium gallium selenide sizing agent, wherein the binary selenides can be two bronze medal selenium (Cu 2Se), a bronze medal selenium (CuSe), two indiumizations, three selenium (In 2Se 3), two galliumizations, three selenium (Ga 2Se 3), indium selenium (InSe), gallium selenium (GaSe) one of them.

The concocting method of aforesaid anti-vacuum manufacture copper indium gallium selenide sizing agent, wherein the ternary selenides can be copper indium diselenide (CuInSe) or copper selenide gallium (CuGaSe) one of them.

The concocting method of aforesaid anti-vacuum manufacture copper indium gallium selenide sizing agent, wherein sheeting accounts for the volume ratio of total material less than 50%.

The concocting method of aforesaid anti-vacuum manufacture copper indium gallium selenide sizing agent, wherein said solvent comprise alcohols, ethers, ketone or mix above-mentioned more than two kinds solvent at least one of them.

The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, the concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent of the present invention has following advantage and beneficial effect at least:

One, the present invention saves equipment cost owing to do not use the high temperature reduction method.

Two, the present invention has avoided using dangerous hydrogen selenide owing to do not use the selenizing method.

Three, the present invention has improved the compactness of institute's produced film owing to use difform particle.

In sum, the present invention has obvious improvement technically, has tangible good effect, really is a new and innovative, progressive, practical new design.

Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.

Description of drawings

Fig. 1 is the Copper Indium Gallium Selenide of existing located by prior art or the schematic diagram of Copper Indium Gallium Selenide (sulphur) solar battery structure.

Fig. 2 is the schematic diagram of the concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent of the present invention.

Embodiment

Reach technological means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, its embodiment of concocting method, method, step, feature and the effect thereof of the anti-vacuum manufacture copper indium gallium selenide sizing agent that foundation the present invention is proposed, describe in detail as after.

Relevant aforementioned and other technology contents, characteristics and effect of the present invention can be known to present in the following detailed description that cooperates with reference to graphic preferred embodiment.By the explanation of embodiment, when can being to reach technological means that predetermined purpose takes and effect to obtain one more deeply and concrete understanding to the present invention, yet appended graphic only provide with reference to the usefulness of explanation, be not to be used for the present invention is limited.

See also shown in Figure 2ly, Fig. 2 is the schematic diagram of the concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent of the present invention.The concocting method of anti-vacuum manufacture Copper Indium Gallium Selenide of the present invention (sulphur) slurry is execution in step S10 at first, the formula rate of computation requirement Copper Indium Gallium Selenide (sulphur), mix and use binary or the ternary selenide material that contains IB, IIIA family, wherein contain and be no more than 50% lamellar material at the most, the ratio of the IB that formula rate comprised, IIIA family element and the selenium element of Copper Indium Gallium Selenide (sulphur) is IB: IIIA: the not ear ratio=0.9-1.0 of selenium element: 1.0: 2.0.Wherein IB family element can be copper, and IIIA family element can be pure indium, pure gallium or mixes the material of indium and gallium, and the binary selenide material for example is two bronze medal selenium (Cu 2Se), a bronze medal selenium (CuSe), two indiumizations, three selenium (In 2Se 3), two galliumizations, three selenium (Ga 2Se 3), indium selenium (InSe) or gallium selenium (GaSe) etc., the ternary selenides then for example is copper indium diselenide (CuInSe) or copper selenide gallium (CuGaSe), pore volume significantly was contracted to below 25% when the sheet-containing material can make film forming.

Then execution in step S20 adds single solvent such as alcohols, ethers or ketone or mixes two or more two kinds mixed solvents as mixed media.

Last execution in step S30 adds stirring to finish the allotment of slurry, as the material of light-absorbing precursor layer as NaI or interfacial agent of different nature.

Above-mentioned slurry with antivacuum rubbing method, is coated on the substrate that contains bottom electrode as electrodeposition process, scraper rubbing method, slot coated method, wire mark method or ultrasonic waves rubbing method etc., and soft roasting removal solvent is to form precursor layer.

Make it form light absorbing zone with 400-800 ℃ of long crystalline substance of high temperature of RTA stove precursor layer again, in addition in the high temperature RTA process, the selenium composition may reduce, can in the RTA process, add pure VIA family element powders, it can be the selenium powder and the sulphur powder of selenium powder, sulphur powder or mixing, powder is volatilized in high temperature form VIA family steam, the selenium composition of replenish lost makes the ratio that contains IB, IIIA and VIA family element in the precursor layer still maintain IB: IIIA: the not ear ratio=0.9-1.0 of VIA family element: 1.0: 2 optimal proportion.

The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be not break away from the technical solution of the present invention content, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.

Claims (6)

1. the concocting method of an anti-vacuum manufacture copper indium gallium selenide sizing agent is characterized in that it is in order to making a copper indium gallium selenide sizing agent under non-vacuum environment, and this copper indium gallium selenide sizing agent is to form an absorbed layer in order to be coated on the molybdenum layer, and this method may further comprise the steps:
At first, according to a formula rate, mix chip shape and contain the binary or the ternary selenide material of IB, IIIA family element, forming an original mixed powder, and this IB family element comprises copper, and this IIIA family element comprises indium or gallium or indium gallium composite material;
Then, add solvent as mixed media; And
At last, interpolation interfacial agent or solid also stirs to finish the allotment of slurry, uses forming the copper indium gallium selenide sizing agent that contains IB, IIIA family and selenium element.
2. the concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent according to claim 1, the formula rate that it is characterized in that wherein said original mixed powder are that the not ear ratio that comprises this IB, IIIA family element and selenium element equals 0.9-1.0: 1.0: 2.0.
3. the concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent according to claim 1, it is characterized in that wherein the binary selenides be two bronze medal selenium, a bronze medal selenium, two indiumizations, three selenium, two galliumizations, three selenium, indium selenium, gallium selenium one of them.
4. the concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent according to claim 1, it is characterized in that wherein the ternary selenides be copper indium diselenide or copper selenide gallium one of them.
5. the concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent according to claim 1 is characterized in that wherein sheeting accounts for the volume ratio of total material less than 50%.
6. the concocting method of anti-vacuum manufacture copper indium gallium selenide sizing agent according to claim 1, it is characterized in that wherein said solvent comprise alcohols, ethers, ketone or mix above-mentioned more than two kinds solvent at least one of them.
CN201010111478A 2010-02-11 2010-02-11 Preparation method for anti-vacuum manufacture of copper-indium-gallium-selenium slurry CN101840957A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101159298A (en) * 2007-11-22 2008-04-09 北京科技大学 Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer
US7521344B2 (en) * 2001-04-16 2009-04-21 Basol Bulent M Method of forming semiconductor compound film for fabrication of electronic device and film produced by same using a solid solution
CN101531529A (en) * 2009-04-14 2009-09-16 武汉理工大学 Preparation method of CuInxGa1-xSe2 powder
JP2009540537A (en) * 2006-02-23 2009-11-19 ファン デューレン、イェルーン カー.イェー.VAN DUREN Jeroen K.J. High throughput semiconductor precursor layer printing with intermetallic microflake particles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7521344B2 (en) * 2001-04-16 2009-04-21 Basol Bulent M Method of forming semiconductor compound film for fabrication of electronic device and film produced by same using a solid solution
JP2009540537A (en) * 2006-02-23 2009-11-19 ファン デューレン、イェルーン カー.イェー.VAN DUREN Jeroen K.J. High throughput semiconductor precursor layer printing with intermetallic microflake particles
CN101159298A (en) * 2007-11-22 2008-04-09 北京科技大学 Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer
CN101531529A (en) * 2009-04-14 2009-09-16 武汉理工大学 Preparation method of CuInxGa1-xSe2 powder

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Application publication date: 20100922