CN101820031A - Manufacturing method of copper indium gallium selenium and/or sulfur light absorption preformed layer without adhesive and active agent - Google Patents
Manufacturing method of copper indium gallium selenium and/or sulfur light absorption preformed layer without adhesive and active agent Download PDFInfo
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- CN101820031A CN101820031A CN201010111497A CN201010111497A CN101820031A CN 101820031 A CN101820031 A CN 101820031A CN 201010111497 A CN201010111497 A CN 201010111497A CN 201010111497 A CN201010111497 A CN 201010111497A CN 101820031 A CN101820031 A CN 101820031A
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- indium gallium
- copper indium
- gallium selenide
- sulphur
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- Y—GENERAL 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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a manufacturing method of a copper indium gallium selenium and/or sulfur light absorption preformed layer, in particular to a manufacturing method of the copper indium gallium selenium and/or sulfur light absorption preformed layer without an adhesive and an active agent, which comprises the following steps: (1) mixing two, three or four components of IB, IIIA and VIA group elements, and forming a first mixed powder and a second mixed powder; (2) adding VIA group element powder to the first mixed powder to form a third mixed powder; (3) adding solvents to the second mixed powder and the third mixed powder and respectively grinding into first slurry and second slurry; (4,5) coating the first slurry and the second slurry sequentially on a molybdenum layer to form a first copper indium gallium selenium and/or sulfur layer and a second copper indium gallium selenium and/or sulfur layer; and (6) softly baking to form the copper indium gallium selenium and/or sulfur light absorption preformed layer. An interfacial active agent is not used to avoid reduction of the solar battery efficiency caused by residual carbon and oxygen.
Description
Technical field
The present invention relates to the manufacture method of a kind of Copper Indium Gallium Selenide and/or sulfur light absorption preformed layer, particularly a kind ofly be used for the antivacuum adhesive-free of even light absorption preformed layer and the Copper Indium Gallium Selenide and/or the sulfur light absorption preformed layer manufacture method of activating agent of on molybdenum layer, forming down.
Background technology
In recent years, the new line of and environmental consciousness surging with international oil price, green energy resource has become the new forms of energy main flow, 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, and pour into a large amount of development costs and subsidies granted for policy considerations invariably, 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 the highest (element cell can be up to 20% with the conversion efficiency of Copper Indium Gallium Selenide or Copper Indium Gallium Selenide (sulphur) solar cell again, and module about 14%), therefore come into one's own especially.
Consult Fig. 1; the copper indium gallium selenium solar cell structure of prior art comprises substrate 10; first conductive layer 20; Copper Indium Gallium Selenide and/or 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; corrosion resistant plate or plastic plate; first conductive layer 20 generally comprises metal molybdenum; as backplate; Copper Indium Gallium Selenide and/or sulphur absorbed layer 30 comprise the copper of proper proportion; indium; gallium and selenium; as p type film; be main light absorbed layer; resilient coating 40 comprises cadmium sulfide (CdS); 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 and/or sulphur solar cell mainly is divided into vacuum manufacture method and antivacuum manufacture method according to the manufacturing environment of Copper Indium Gallium Selenide and/or sulphur absorbed layer.The vacuum manufacture method 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.Antivacuum manufacture method comprises print process or electrodeposition process, shortcoming be technology that is that all right is ripe, no larger area commercial prod.But antivacuum manufacture method has the advantage that manufacturing equipment is simple and process conditions are reached easily, and suitable business potential is arranged.
The antivacuum manufacture method of Copper Indium Gallium Selenide and/or sulphur absorbed layer is to allocate Copper Indium Gallium Selenide and/or sulphur slurry or ink (Ink) earlier, in order to be applied on the molybdenum substrate.
In the prior art, Copper Indium Gallium Selenide and/or sulphur slurry preparation are to mix the powder of two compositions, three compositions or four compositions that contain IB, IIIA and VIA family element to form the original powder that contains Copper Indium Gallium Selenide and/or sulphur with proper proportion earlier, add the solvent of proper proportion again, and stir to form original Copper Indium Gallium Selenide and/or sulphur slurry, add bonding agent (binder) or interfacial agent cementability at last, and mix to form last Copper Indium Gallium Selenide and/or sulphur slurry with raising Copper Indium Gallium Selenide and/or sulphur absorbed layer and molybdenum backplate.
The shortcoming of above-mentioned prior art is, bonding agent, interfacial agent may remain in last Copper Indium Gallium Selenide and/or the sulphur absorbed layer, cause the phosphorus content and the oxygen content of Copper Indium Gallium Selenide and/or sulphur absorbed layer higher, influence the optical absorption characteristics of Copper Indium Gallium Selenide and/or sulphur absorbed layer, even influence efficient.
Therefore, need a kind of Copper Indium Gallium Selenide and/or sulphur slurry preparation method of not adding bonding agent, interfacial agent, to improve above-mentioned prior art problems.
Summary of the invention
The objective of the invention is to, overcome existing making Copper Indium Gallium Selenide and/or the existing defective of sulfur light absorption preformed layer, and the Copper Indium Gallium Selenide and/or the sulfur light absorption preformed layer manufacture method of a kind of adhesive-free and activating agent are provided.Thereby avoid residuing in bonding agent, interfacial agent in the light absorbing zone, cause the phosphorus content and the oxygen content of Copper Indium Gallium Selenide and/or sulphur absorbed layer higher, influence the optical absorption characteristics and the conversion efficiency of Copper Indium Gallium Selenide and/or sulphur absorbed layer
The object of the invention to solve the technical problems is to adopt following technical scheme to realize.According to a kind of adhesive-free of the present invention's proposition and the Copper Indium Gallium Selenide and/or the sulfur light absorption preformed layer manufacture method of activating agent, comprise the following steps:
(1) according to formula rate, two compositions, three compositions or four composition powder that allotment contains IB, IIIA and VIA family element contain Copper Indium Gallium Selenide and/or sulphur mixed-powder to form first and second;
(2) contain Copper Indium Gallium Selenide and/or sulphur mixed-powder with original VIA element ratio with first, add extra VIA family element powders again to this original mixed powder, and mix to form the 3rd and contain Copper Indium Gallium Selenide and/or sulphur mixed-powder;
(3) containing Copper Indium Gallium Selenide and/or sulphur mixed-powder with the second and the 3rd adds easy volatile solvent and grinds to form first and second Copper Indium Gallium Selenide and/or sulphur slurry respectively with nano-milled machine.
(4) first Copper Indium Gallium Selenide and/or sulphur slurry are coated on the molybdenum layer, form first Copper Indium Gallium Selenide and/or sulphur layer;
(5) second Copper Indium Gallium Selenide and/or sulphur slurry are coated on formation second Copper Indium Gallium Selenide and/or sulphur layer on first Copper Indium Gallium Selenide and/or the sulphur layer;
(6) the soft roasting solvent evaporates that makes forms Copper Indium Gallium Selenide and/or sulfur light absorption preformed layer.
Purpose of the present invention and solve its technical problem and can also be further achieved by the following technical measures.
The Copper Indium Gallium Selenide of aforesaid adhesive-free and activating agent and/or sulfur light absorption preformed layer manufacture method, wherein said IB family element comprises copper.
The Copper Indium Gallium Selenide of aforesaid adhesive-free and activating agent and/or sulfur light absorption preformed layer manufacture method, wherein said IIIA family element comprises indium or gallium or indium gallium composite material.
The Copper Indium Gallium Selenide of aforesaid adhesive-free and activating agent and/or sulfur light absorption preformed layer manufacture method, wherein said VI family element can be selenium or sulphur or selenium sulphur composite material.
The Copper Indium Gallium Selenide of aforesaid adhesive-free and activating agent and/or sulfur light absorption preformed layer manufacture method, wherein said solvent comprise alcohols, ethers, ketone or mix described more than two kinds solvent at least one of them.
The Copper Indium Gallium Selenide of aforesaid adhesive-free and activating agent and/or sulfur light absorption preformed layer manufacture method, wherein said first and second contain the IB of Copper Indium Gallium Selenide and/or sulphur mixed-powder: IIIA: the molar ratio of VI element=1.0: 1.0: 2.0.
The Copper Indium Gallium Selenide of aforesaid adhesive-free and activating agent and/or sulfur light absorption preformed layer manufacture method, the wherein said the 3rd contains the IB of Copper Indium Gallium Selenide and/or sulphur mixed-powder: IIIA: the molar ratio of VI element=1.0: 1.0: X, wherein X is between 2.0～4.0.
When the present invention mainly utilizes allotment Copper Indium Gallium Selenide and/or sulphur slurry, except the Copper Indium Gallium Selenide and/or sulphur compound of the normal ratio of original use, add excessive VIA family element powders in addition, except that the content that can replenish VIA family element, the interfacial agent and the bonding agent that also can replace former use, slurry is coated with into two-layer above coating can makes the compound that contains IB/IIIA/VIA be easy to spread and react, generate the Copper Indium Gallium Selenide of yellow copper structure and/or the light absorbing zone of sulphur.
The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, the Copper Indium Gallium Selenide of adhesive-free of the present invention and activating agent and/or sulfur light absorption preformed layer manufacture method can reach suitable technological progress and practicality, and have the extensive value on the industry, and it has following advantage at least:
1, do not use interfacial agent can avoid residual carbon containing and oxygen interface activating agent, avoid reducing solar battery efficiency.
2, slurry being coated with into two-layer above coating can make the compound that contains IB/IIIA/VIA be easy to spread and be reacted into the Copper Indium Gallium Selenide of yellow copper structure and/or the light absorbing zone of sulphur.
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 selenium solar cell structural representation of prior art.
Fig. 2 is the Copper Indium Gallium Selenide and/or the sulfur light absorption preformed layer manufacture method block diagram of adhesive-free of the present invention and activating agent.
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, the adhesive-free that foundation the present invention is proposed and Copper Indium Gallium Selenide and/or its embodiment of sulfur light absorption preformed layer manufacture method, structure, feature and the effect thereof of activating agent, describe in detail as after.
Relevant aforementioned and other technology contents, characteristics and effect of the present invention can clearly present in the detailed description of the preferred embodiment of following conjunction with figs..By the explanation of embodiment, when can being to reach technological means that predetermined purpose takes and effect to get one more deeply and concrete understanding to the present invention, yet accompanying drawing 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, a kind of adhesive-free of preferred embodiment of the present invention and the Copper Indium Gallium Selenide of activating agent and/or sulfur light absorption preformed layer manufacture method comprise the following steps:
(1) according to formula rate, two compositions, three compositions or four composition powder that allotment contains IB, IIIA and VIA family element contain Copper Indium Gallium Selenide and/or sulphur mixed-powder to form first and second;
(2) contain Copper Indium Gallium Selenide and/or sulphur mixed-powder with original VIA element ratio with first, add extra VIA family element powders again to this original mixed powder, and mix to form the 3rd and contain Copper Indium Gallium Selenide and/or sulphur mixed-powder, make the total VIA family element ratio after the two-layer above coating of last coating be increased to VIA/IB ratio＞2.
(3) containing Copper Indium Gallium Selenide and/or sulphur mixed-powder with the second and the 3rd adds easy volatile solvent and grinds to form first and second Copper Indium Gallium Selenide and/or sulphur slurry respectively with nano-milled machine.Specifically be, the aluminium oxide of use 1～5mm large scale or zirconium oxide abrasive ball and low temperature easy volatile solvent are roughly ground earlier, change the aluminium oxide of small scale 0.1～0.5mm size more or zirconium oxide abrasive ball and low temperature easy volatile solvent again and be ground to the following nanometer powder slurry of 500nm together, the nanometer powder slurry more than two kinds that has mixed can be directly as the Copper Indium Gallium Selenide and/or the sulphur slurry of coating usefulness.
(4) first Copper Indium Gallium Selenide and/or sulphur slurry are coated on the molybdenum layer, form first Copper Indium Gallium Selenide and/or sulphur layer;
(5) second Copper Indium Gallium Selenide and/or sulphur slurry are coated on formation second Copper Indium Gallium Selenide and/or sulphur layer on first Copper Indium Gallium Selenide and/or the sulphur layer;
(6) the soft roasting solvent evaporates that makes forms Copper Indium Gallium Selenide and/or sulfur light absorption preformed layer.
Described IB family element comprises copper.
Described IIIA family element comprises indium or gallium or indium gallium composite material.
Described VI family element can be selenium or sulphur or selenium sulphur composite material.
Described solvent comprise alcohols, ethers, ketone or mix described more than two kinds solvent at least one of them.
Described first and second contain the IB of Copper Indium Gallium Selenide and/or sulphur mixed-powder: IIIA: the molar ratio of VI element=1.0: 1.0: 2.0.The ratio that is Copper Indium Gallium Selenide and/or the original total formula rate of the sulphur IB, the IIIA that are comprised and VIA family element is the molar ratio=1.0: 1.0: 2.0 of IB: IIIA: VI.Wherein IIIA family element is pure indium, the material of pure gallium or mixing indium and gallium, VIA family element is a pure selenium in addition, the material of bright sulfur or mixing selenium and sulphur, the extra VI family element powders that adds, the IB that last Copper Indium Gallium Selenide and/or sulphur mixing preformed layer are comprised, the ratio of IIIA and VIA family element is the molar ratio=1.0: 1.0 of IB: IIIA: VI: X, and X is between 2.0 to 4.0, when additionally the ratio of the powder of interpolation VIA family element is too low, there is not adhesive effect, contain the ratio of VIA family element powders when too high, reduce Copper Indium Gallium Selenide and/or sulphur absorbed layer on the contrary to the bonding force that molybdenum layer produced, the ratio that therefore contains VIA family element powders need be controlled in above-mentioned preferred range.
Concrete coating process is as follows: the slurry that will not contain excessive VIA element is earlier coated on the substrate that contains bottom electrode, (for example original individual layer can be applied to coating about 2～3 μ m to the formation ground floor coating thin than signal layer coating, if three layers of desire coatings, then every layer is coated with about 0.7～1.0 μ m instead), the slurry that will contain excessive VIA element is again coated on the substrate that contains the ground floor coating, if any the slurry that does not contain excessive VIA element more than the third, coat on the substrate successively again, make final coating layer thickness and original signal layer coating similar thickness, carry out soft roasting at last again, make the formation light absorption preformed layer, the Copper Indium Gallium Selenide and/or the sulfur light absorption preformed layer that contain two-layer above coating layer, can be than the thicker preformed layer of individual layer, in the long fast brilliant process of short annealing heat treatment (RTA), VIA family element is being coated with inter-level diffusion more up and down with the formation yellow copper structure, and has the Copper Indium Gallium Selenide and/or the sulphur light absorbing zone of cementability, is attached on the lower electrode layer.
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 the content that does not break away from technical solution of the present invention, 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 (7)
1. the Copper Indium Gallium Selenide and/or the sulfur light absorption preformed layer manufacture method of adhesive-free and activating agent, in order to form even light absorption preformed layer down antivacuum on molybdenum layer, this method comprises:
(1) according to formula rate, two compositions, three compositions or four composition powder that allotment contains IB, IIIA and VIA family element contain Copper Indium Gallium Selenide and/or sulphur mixed-powder to form first and second;
(2) contain Copper Indium Gallium Selenide and/or sulphur mixed-powder with original VIA element ratio with first, add extra VIA family element powders again to this original mixed powder, and mix to form the 3rd and contain Copper Indium Gallium Selenide and/or sulphur mixed-powder;
(3) containing Copper Indium Gallium Selenide and/or sulphur mixed-powder with the second and the 3rd adds easy volatile solvent and grinds to form first and second Copper Indium Gallium Selenide and/or sulphur slurry respectively with nano-milled machine;
(4) first Copper Indium Gallium Selenide and/or sulphur slurry are coated on the molybdenum layer, form first Copper Indium Gallium Selenide and/or sulphur layer;
(5) second Copper Indium Gallium Selenide and/or sulphur slurry are coated on formation second Copper Indium Gallium Selenide and/or sulphur layer on first Copper Indium Gallium Selenide and/or the sulphur layer;
(6) the soft roasting solvent evaporates that makes forms Copper Indium Gallium Selenide and/or sulfur light absorption preformed layer.
2. the Copper Indium Gallium Selenide of adhesive-free according to claim 1 and activating agent and/or sulfur light absorption preformed layer manufacture method is characterized in that described IB family element comprises copper.
3. the Copper Indium Gallium Selenide of adhesive-free according to claim 1 and activating agent and/or sulfur light absorption preformed layer manufacture method is characterized in that described IIIA family element comprises indium or gallium or indium gallium composite material.
4. the Copper Indium Gallium Selenide of adhesive-free according to claim 1 and activating agent and/or sulfur light absorption preformed layer manufacture method is characterized in that described VI family element can be selenium or sulphur or selenium sulphur composite material.
5. the Copper Indium Gallium Selenide of adhesive-free according to claim 1 and activating agent and/or sulfur light absorption preformed layer manufacture method, it is characterized in that described solvent comprise alcohols, ethers, ketone or mix described more than two kinds solvent at least one of them.
6. the Copper Indium Gallium Selenide of adhesive-free according to claim 1 and activating agent and/or sulfur light absorption preformed layer manufacture method is characterized in that described first and second contain the IB of Copper Indium Gallium Selenide and/or sulphur mixed-powder: IIIA: the molar ratio of VI element=1.0: 1.0: 2.0.
7. the Copper Indium Gallium Selenide of adhesive-free according to claim 1 and activating agent and/or sulfur light absorption preformed layer manufacture method, it is characterized in that the described the 3rd contains the IB of Copper Indium Gallium Selenide and/or sulphur mixed-powder: IIIA: the molar ratio of VI element=1.0: 1.0: X, wherein X is between 2.0～4.0.
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Cited By (1)
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| CN102254999A (en) * | 2010-12-29 | 2011-11-23 | 友达光电股份有限公司 | Method for manufacturing solar cell |
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| CN101443130A (en) * | 2006-02-23 | 2009-05-27 | 耶罗恩·K·J·范杜伦 | High-throughput formation of semiconductor layer by use of chalcogen and inter-metallic material |
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| US20060178012A1 (en) * | 2001-04-16 | 2006-08-10 | Basol Bulent M | Method of Forming Semiconductor Compound Film for Fabrication of Electronic Device and Film Produced By Same |
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Application publication date: 20100901 |