CN101245443A - Target material and thin membrane manufactured with the target material - Google Patents
Target material and thin membrane manufactured with the target material Download PDFInfo
- Publication number
- CN101245443A CN101245443A CN 200710078740 CN200710078740A CN101245443A CN 101245443 A CN101245443 A CN 101245443A CN 200710078740 CN200710078740 CN 200710078740 CN 200710078740 A CN200710078740 A CN 200710078740A CN 101245443 A CN101245443 A CN 101245443A
- Authority
- CN
- China
- Prior art keywords
- target
- iiia
- powder
- alloy
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention mainly provides a target, the elemental composition of which is IBx-IIIAy-VIAz, wherein, IB is selected from at least one of the group as follows: Cu and Ag; IIIA is selected form at least one of the group as follows: In and Ga; VIA is selected from as least one of the group as follows: S, Se and Te; x, y and z are respectively atomic percents of contents of IB, IIIA and VIA while the x is more than or equal to 0 and less than 1, so is the y, the z is more than 0 and less than 1 and the sum of the x, the y and the z is equal to 1; the production method of the target comprises: pre-alloy is formed: the pre-alloy is synthesized by one element of the target and more than one other element in the elemental composition of the target; powder production: the pre-alloy is produced to be powder; powder mix: the powder is directly mixed or mixed with powder of other elements or pre-alloy powder; sintering: the powder mixture forms the target after sintering. The invention also provides a thin-film used in solar battery, which is made by sputtering the target.
Description
Technical field
The present invention mainly is about a kind of target, refers in particular to the elementary composition target of a kind of IB-IIIA-VIA of having, and it can be applicable to the film that sputter is made solar cell.
Background technology
In the epoch that fossil fuel lacks gradually, add that problems such as global climate transition and atmospheric pollution are serious day by day, the application of alternative energy more and more is subjected to people and payes attention to, and wherein solar cell (solarcell) can provide potentiality cheap and continuously electric power to be gazed at because of having.In the present product, solar cell can be divided into roughly:
(1) chip-shaped (wafer type) solar cell: comprise monocrystalline (single crystal) silicon and polycrystalline (polycrystalline) silicon; And
(2) film-type (thin film type) solar cell.
Though silicon type solar cell is the existing market main flow,, therefore need thicker silicon materials as absorption layer (absorber) because of it is indirect gap (indirectenergy gap); And it is elementary composition (as CuInGaSe to have IB-IIIA-VIA in the thin film solar cell
2CIGS) material is direct gap (direct energy gap), and the assimilated efficiency of light is very high, add the size that to adjust energy gap by the In/Ga components in proportions, therefore only need very thin layer of material can produce high-photoelectric transformation efficiency, so can significantly save material, reduce the solar cell cost of manufacture.Therefore have the elementary composition solar cell of IB-IIIA-VIA and be the splendid product of malleability before following.
The production method of CIGS film has chemical Vapor deposition process (CVD, chemical vapordeposition, disclose as No. 5474939 patent of United States Patent (USP)), physical vaporous deposition (PVD, physical vapor deposition discloses as No. 5141564 patent of United States Patent (USP)) and liquid phase deposition (LPE, liquid phase deposition) etc.; The sputtering method (sputter) that wherein belongs to physical vaporous deposition is for providing the method that technology is cheap and film characteristics is good, but do not have the CIGS sputtered target material (target) that the tool complete element is formed at present, so the CIGS film also can't be directly with the sputtering method manufacturing.
The manufacture method of CIGS film is prior to depositing precursor (precursor) on the substrate at present, thermal chemical reaction via selenizing (selenization) technology forms CIGS film (disclosing as Japanese 10-135495 patent) again, yet this technology is quite loaded down with trivial details.
In addition, in Japanese 2000-73163 patent, obtain people such as a former pure youth and utilize casting (casting) method to make Cu-Ga (copper-gallium) alloy target material, make the Cu-Ga alloy of tool fragility (brittle) in process of cooling, can not split by the control rate of temperature fall; In addition, in No. 1719626 patent of China, people such as Zhuan Daming also use forging type to make the Cu-Ga alloy target material.Though casting can obtain the target of high-density and low oxygen content, but when this copper gallium binary alloy is applied to make the absorption layer of solar cell, need to use more numerous and diverse common sputter (Co-sputtering) or multiple tracks sputter (multi-sputtering) program, even also need add selenizing (selenization) method, so just can produce the alloy firm of CIGS series, thus also quite complicated on the technology; In addition, during melting (melting) Cu-Ga binary alloy,, make that the composition of foundry goods (ingot) is wayward because of the vapour pressure of Ga is very high; Moreover, casting can derive shrinkage cavity (shrinkage) and component segregation problems such as (segregation).
In sum, how to make IB-IIIA-VIA target and make the critical bottleneck of CIGS solar cell for using sputtering process with complete element composition, if a CIGS target that contains complete composition can be provided, then can significantly reduce process complexity, also can reduce the manufacturing cost of solar cell.
Summary of the invention
Because the manufacture craft of existing CIGS film is quite loaded down with trivial details, the object of the present invention is to provide a kind of target, it can be applicable to make has the elementary composition film of IB-IIIA-VIA.
Another object of the present invention is to provide a kind of film with this target made, it can be applicable on the solar cell, and manufacturing cost that can be cheaper is made solar cell.
For reaching described purpose, the elementary composition of first kind of target of the present invention is IB
x-IIIA
y-VIA
z
Wherein,
IB is selected from least a in the following group: Cu and Ag;
IIIA is selected from least a in the following group: In and Ga;
VIA is selected from least a in the following group: S, Se and Te;
X is that the atomic percent of IB content, atomic percent, the z that y is IIIA content are the atomic percent of VIA content, and satisfies 0≤x＜1,0＜y＜1,0＜z＜1, x+y+z=1.
Second kind of target of the present invention, it is elementary composition to be IB
x-IIIA
y-VIA
zWherein,
IB is selected from least a in the following group: Cu and Ag;
IIIA is selected from least a in the following group: In and Ga;
VIA is selected from least a in the following group: S, Se and Te;
X is that the atomic percent of IB content, atomic percent, the z that y is IIIA content are the atomic percent of VIA content, and satisfies 0＜x＜1,0≤y＜1,0＜z＜1, x+y+z=1.
The making method of target of the present invention comprises following steps:
Form prealloy: more than one other element in a target elements and the target elements composition is synthesized prealloy;
Make powder: prealloy is made powder;
Mix powder: described powder is directly mixed or mix with other element or pre-alloyed powder in the target elements composition again;
Sintering: mixed powder forms target behind sintering.
Film of the present invention is to use above-mentioned target sputter to form.
Above-mentioned film can be used for solar cell.
The attainable concrete effect of the present invention comprises:
1. it is elementary composition that target of the present invention has complete IB-IIIA-VIA, therefore with this target via once sputtering process, can coat and have the elementary composition film of complete IB-IIIA-VIA, this film can directly apply in the solar cell, avoid existing CIGS film to need to handle the problem that to make, significantly reduce the complexity of film producing process and the manufacturing cost of solar cell through multiple sputter or selenizing.
2. the present invention is in the manufacturing processed of target, forms prealloy earlier, therefore after sintering process in, can not make a variation and the destructive phenomenon because of the material fusion produces material composition, not guarantee the fine quality of target of the present invention.
Description of drawings
Fig. 1 is a schema of the present invention.
Embodiment
First kind of target of the present invention, it is elementary composition to be IB
x-IIIA
y-VIA
zWherein,
IB is selected from least a in the following group: Cu (copper) and Ag (silver);
IIIA is selected from least a in the following group: In (indium) and Ga (gallium);
VIA is selected from least a in the following group: S (sulphur), Se (selenium) and Te (tellurium);
X is that the atomic percent of IB content, atomic percent, the z that y is IIIA content are the atomic percent of VIA content, and satisfies 0≤x＜1,0＜y＜1,0＜z＜1, and x+y+z=1.
Second kind of target of the present invention, it is elementary composition to be IB
x-IIIA
y-VIA
zWherein,
IB is selected from least a in the following group: Cu and Ag;
IIIA is selected from least a in the following group: In and Ga;
VIA is selected from least a in the following group: S, Se and Te;
X is that the atomic percent of IB content, atomic percent, the z that y is IIIA content are the atomic percent of VIA content, and satisfies 0＜x＜1,0≤y＜1,0＜z＜1, x+y+z=1.
When containing the elementary composition target of IB-IIIA-VIA in manufacturing, all very low (the IIIA for example fusing point of In is 156.6 ℃, and the fusing point of Ga is 29.9 ℃ because IIIA and VIA are used to make the fusing point of element of target; The VIA for example fusing point of S is 112.8 ℃, the fusing point of Se is 217 ℃, the fusing point of Te is 449.5 ℃), so its vapour pressure is very high, and the fusing point of IB element very high for IIIA and VIA (for example the fusing point of Cu is 1084.6 ℃, and the fusing point of Ag is 961.9 ℃), therefore, if the simple melting technology of using is made this IB-IIIA-VIA multi-element compounds target, and is not easy the good ingot casting of acquired character.
If single mode of powder metallurgy (powder metallurgy) of using is made IB-IIIA-VIA series target, also the fusing point because of IIIA and VIA is all very low, and the fusing point of IB element is very high for IIIA and VIA, when if the element powders of IB and IIIA and VIA carries out sintering (sintering), for example use hot pressing (HP, hot pressing) or heat when all pressing (HIP, hot isostatic pressing), then low-melting element can fusion and cause material damage.
Because the target and the castmethod of powder metallurgy process made are compared, its target quality is preferable, so the present invention is to use powder metallurgy to make the elementary composition target of IB-IIIA-VIA.In being formed, a target elements and target elements during more than one other element synthetic compound, generally this compound is referred to as prealloy.Again this prealloy directly or is again added the technology that other target elements is carried out powder metallurgy, can make target of the present invention.
The making method of target of the present invention is as follows, and its step please refer to shown in Figure 1.
Form prealloy: more than one other element in a target elements and the target elements composition is synthesized prealloy, and this prealloy synthetic mode can be melting, thermal chemical reaction or other method.
Make powder: prealloy is made powder, and the production method of powder can adopt mechanical means, as with after the prealloy crushing or smashing, grind with ball milling or rod milling again, or other physico-chemical process such as atomization (atomization) etc.
Mix powder: described powder is directly mixed or mix with other element powders or pre-alloyed powder in the target elements composition again;
Sintering: mixed powder forms the target of tool good characteristic behind sintering, and the sintering of mixed powder can be adopted pressure sintering, hot isostatic pressing or pressure sintering and merge hot isostatic pressing and carry out, this target can be again through shaping target for using for the sputter machine.
First kind of target of the present invention can comprise following various target:
When x is 0,0.5＜z＜0.6, IIIA is In-Ga, and VIA is Se, can obtain the In-Ga-Se target.
When IB is Cu, Ag or Cu-Ag, IIIA is In-Ga, and VIA is Se, can obtain Cu-In-Ga-Se, Ag-In-Ga-Se or Cu-Ag-In-Ga-Se target.
When IB is Cu, Ag or Cu-Ag, IIIA is Ga, and VIA is Se, can obtain Cu-Ga-Se, Ag-Ga-Se or Cu-Ag-Ga-Se target.
When IB is Cu, Ag or Cu-Ag, IIIA is In, and VIA is Se, can obtain Cu-In-Se, Ag-In-Se or Cu-Ag-In-Se target.
When x is 0,0.428＜z＜0.6, IIIA is In, and VIA is Se, can obtain the In-Se target.
When x is 0,0.5＜z＜0.6, IIIA is In-Ga, and VIA is S, can obtain the In-Ga-S target.
When IB is Cu, Ag or Cu-Ag, IIIA is In-Ga, and VIA is S, can obtain Cu-In-Ga-S, Ag-In-Ga-S or Cu-Ag-In-Ga-S target.
When x is 0,0.5＜z＜0.6, IIIA is In-Ga, and VIA is Te, can obtain the In-Ga-Te target.
When IB is Cu, IIIA is In-Ga, and VIA is Te, can obtain the Cu-In-Ga-Te target.
When IB is Cu, IIIA is In, and VIA is Te, can obtain the Cu-In-Te target.
By above-mentioned making method, can produce and have the elementary composition target of complete IB-IIIA-VIA.And since target of the present invention to have a complete IB-IIIA-VIA elementary composition, therefore with this target via once sputtering process, can coat and have the elementary composition film of complete IB-IIIA-VIA, can directly apply in the solar cell, avoid existing CIGS film to need to handle the problem that to make, significantly reduce the manufacturing cost of solar cell through multiple sputter and/or selenizing.
Claims (13)
1. target, it is elementary composition to be IB
x-IIIA
y-VIA
zWherein,
IB is selected from least a in the following group: Cu and Ag;
IIIA is selected from least a in the following group: In and Ga;
VIA is selected from least a in the following group: S, Se and Te;
X is that the atomic percent of IB content, atomic percent, the z that y is IIIA content are the atomic percent of VIA content, and satisfies 0≤x＜1,0＜y＜1,0＜z＜1, x+y+z=1.
2. target as claimed in claim 1, x wherein are 0, and IIIA is In-Ga, and VIA is Se.
3. target as claimed in claim 1, IB wherein are Cu, Ag or Cu-Ag, and IIIA is In-Ga, and VIA is Se.
4. target as claimed in claim 1, IB wherein are Cu, Ag or Cu-Ag, and IIIA is Ga, and VIA is Se.
5. target as claimed in claim 1, IB wherein are Cu, Ag or Cu-Ag, and IIIA is In, and VIA is Se.
6. target as claimed in claim 1, x wherein are 0, and IIIA is In, and VIA is Se.
7. target as claimed in claim 1, x wherein are 0, and IIIA is In-Ga, and VIA is S.
8. target as claimed in claim 1, IB wherein are Cu, Ag or Cu-Ag, and IIIA is In-Ga, and VIA is S.
9. target as claimed in claim 1, IB wherein are Cu, and IIIA is In-Ga, and VIA is Te.
10. target as claimed in claim 1, IB wherein are Cu, and IIIA is In, and VIA is Te.
11. a target, it is elementary composition to be IB
x-IIIA
y-VIA
zWherein,
IB is selected from least a in the following group: Cu and Ag;
IIIA is selected from least a in the following group: In and Ga;
VIA is selected from least a in the following group: S, Se and Te;
X is that the atomic percent of IB content, atomic percent, the z that y is IIIA content are the atomic percent of VIA content, and satisfies 0＜x＜1,0≤y＜1,0＜z＜1, x+y+z=1.
12. a film, it is to use as claim 1 or 11 described target sputters and forms.
13. film as claimed in claim 12, it is to be used for solar cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710078740 CN101245443B (en) | 2007-02-17 | 2007-02-17 | Target material and thin membrane manufactured with the target material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710078740 CN101245443B (en) | 2007-02-17 | 2007-02-17 | Target material and thin membrane manufactured with the target material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101245443A true CN101245443A (en) | 2008-08-20 |
| CN101245443B CN101245443B (en) | 2011-05-25 |
Family
ID=39946118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710078740 Expired - Fee Related CN101245443B (en) | 2007-02-17 | 2007-02-17 | Target material and thin membrane manufactured with the target material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101245443B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145385A (en) * | 2010-02-10 | 2011-08-10 | 昆山正富机械工业有限公司 | Method for mixing copper indium gallium selenide slurry without interfacial active agent or solvent |
| CN102630254A (en) * | 2009-11-25 | 2012-08-08 | Aqt太阳能公司 | Low melting point sputter targets for chalcogenide photovoltaic applications and methods of manufacturing the same |
| CN102051584B (en) * | 2009-11-03 | 2012-12-26 | 张昇常 | CIGS solar photoelectric quaternary sputtering target and manufacturing method thereof, method combining CIGS solar photoelectric quaternary sputtering target and target back plate and feeding method for CIGS solar photoelectric quaternary sputtering target |
| CN103108977A (en) * | 2010-09-27 | 2013-05-15 | 吉坤日矿日石金属株式会社 | Cu-In-Ga-Se quaternary alloy sputtering target |
| TWI425978B (en) * | 2010-02-05 | 2014-02-11 | Chung Hsin Lu | Fabrication method for ib-iiia-via powder by the sol-gel method |
| CN106041086A (en) * | 2015-04-09 | 2016-10-26 | 韩国电子通信研究院 | Metal material for 3-dimensional printing, method for manufacturing the same, and method for 3-dimensional printing using the same |
| CN108807572A (en) * | 2018-06-05 | 2018-11-13 | 中山米来机器人科技有限公司 | A kind of silver indium gallium selenium film and its preparation method and application |
| CN114645252A (en) * | 2022-03-01 | 2022-06-21 | 先导薄膜材料（广东）有限公司 | Preparation method of high-purity and high-density GaTe target material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3897622B2 (en) * | 2002-03-18 | 2007-03-28 | 松下電器産業株式会社 | Method for producing compound semiconductor thin film |
| CN100530701C (en) * | 2002-09-30 | 2009-08-19 | 米亚索尔公司 | Manufacturing apparatus and method for large-scale production of thin-film solar cells |
-
2007
- 2007-02-17 CN CN 200710078740 patent/CN101245443B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051584B (en) * | 2009-11-03 | 2012-12-26 | 张昇常 | CIGS solar photoelectric quaternary sputtering target and manufacturing method thereof, method combining CIGS solar photoelectric quaternary sputtering target and target back plate and feeding method for CIGS solar photoelectric quaternary sputtering target |
| CN102630254B (en) * | 2009-11-25 | 2014-07-16 | Aqt太阳能公司 | Low melting point sputter targets for chalcogenide photovoltaic applications and methods of manufacturing the same |
| CN102630254A (en) * | 2009-11-25 | 2012-08-08 | Aqt太阳能公司 | Low melting point sputter targets for chalcogenide photovoltaic applications and methods of manufacturing the same |
| TWI425978B (en) * | 2010-02-05 | 2014-02-11 | Chung Hsin Lu | Fabrication method for ib-iiia-via powder by the sol-gel method |
| CN102145385A (en) * | 2010-02-10 | 2011-08-10 | 昆山正富机械工业有限公司 | Method for mixing copper indium gallium selenide slurry without interfacial active agent or solvent |
| CN103108977B (en) * | 2010-09-27 | 2015-01-21 | 吉坤日矿日石金属株式会社 | Cu-In-Ga-Se quaternary alloy sputtering target |
| CN103108977A (en) * | 2010-09-27 | 2013-05-15 | 吉坤日矿日石金属株式会社 | Cu-In-Ga-Se quaternary alloy sputtering target |
| US9273389B2 (en) | 2010-09-27 | 2016-03-01 | Jx Nippon Mining & Metals Corporation | Cu—In—Ga—Se quaternary alloy sputtering target |
| CN106041086A (en) * | 2015-04-09 | 2016-10-26 | 韩国电子通信研究院 | Metal material for 3-dimensional printing, method for manufacturing the same, and method for 3-dimensional printing using the same |
| US10563292B2 (en) | 2015-04-09 | 2020-02-18 | Electronics And Telecommunications Research Institute | Metal material for 3-dimensional printing, method for manufacturing the same, and method for 3-dimensional printing using the same |
| CN108807572A (en) * | 2018-06-05 | 2018-11-13 | 中山米来机器人科技有限公司 | A kind of silver indium gallium selenium film and its preparation method and application |
| CN108807572B (en) * | 2018-06-05 | 2020-01-17 | 电子科技大学中山学院 | Silver indium gallium selenide thin film and preparation method and application thereof |
| CN114645252A (en) * | 2022-03-01 | 2022-06-21 | 先导薄膜材料（广东）有限公司 | Preparation method of high-purity and high-density GaTe target material |
| CN114645252B (en) * | 2022-03-01 | 2023-11-17 | 先导薄膜材料（广东）有限公司 | Preparation method of high-purity high-density GaTe target material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101245443B (en) | 2011-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101245443B (en) | Target material and thin membrane manufactured with the target material | |
| CN102630254B (en) | Low melting point sputter targets for chalcogenide photovoltaic applications and methods of manufacturing the same | |
| CN100418235C (en) | Cu-Ga alloy target for Cu-In-Ga-Se film solar battery and preparing process thereof | |
| CN101397647B (en) | Cu-In-Ga-Se or Cu-In-Al-Se solar cell absorption layer target material and preparation method thereof | |
| CN102203954A (en) | Chalcogenide alloy sputter targets for photovoltaic applications and methods of manufacturing the same | |
| JP5182494B2 (en) | Manufacturing method of sputtering target for chalcopyrite type semiconductor film formation | |
| CN101260513A (en) | Solar energy battery copper-indium-gallium-selenium film key target material and preparation method thereof | |
| JP2008163367A (en) | Method of manufacturing sputtering target of cu-in-ga-se-based quaternary alloy | |
| CN103205707B (en) | The preparation method of a kind of conductive oxide target and conductive oxide film | |
| WO2013109783A1 (en) | Amalgam method for forming a sputter target useful in the manufacture of thin-film solar photovoltaic cells | |
| CN103510047A (en) | Method for preparing novel conductive indium tin oxide material and film thereof | |
| TW200832727A (en) | Target and thin film fabricated by the target | |
| KR20070008549A (en) | Method for producing a monocrystalline cu(in,ga)se2 powder and mono-grain membrane solar cell containing said powder | |
| JP5418832B2 (en) | Method for producing Cu-In-Ga-Se quaternary alloy sputtering target | |
| CN101736289B (en) | Copper alloy target, manufacturing method thereof and film and solar cell manufactured by same | |
| CN101383384A (en) | Silver copper composite oxide film material for photoelectric semiconductor | |
| Zweigart et al. | CuInSe 2 film growth using precursors deposited at low temperature | |
| CN103626495A (en) | Preparation method for CIGS target material through pressureless sintering | |
| CN115849909B (en) | Copper indium gallium selenium target material, preparation method thereof and solar cell | |
| Londhe et al. | A Novel combined thermal evaporation and solvothermal approach to produce highly crystalline and compact CIG (S1-xSex) 2 thin films | |
| CN110605399A (en) | Preparation method of copper-indium-gallium alloy powder | |
| CN102623571B (en) | Method for producing copper indium gallium diselenide (CIGS) solar battery absorption layer through evaporation method | |
| EP2182083B1 (en) | Copper-gallium alloy sputtering target and method for fabricating the same | |
| CN117185815A (en) | Cu (In, ga, al, ca) Se 2 Preparation process of ceramic target material | |
| CN103887366B (en) | A kind of energy preparation method with adjustable copper indium aluminum selenium membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110525 Termination date: 20150217 |
|
| EXPY | Termination of patent right or utility model |