CN1413947A - Zinc gallium oxide ceramic target material and its preparation method and application - Google Patents
Zinc gallium oxide ceramic target material and its preparation method and application Download PDFInfo
- Publication number
- CN1413947A CN1413947A CN 02156898 CN02156898A CN1413947A CN 1413947 A CN1413947 A CN 1413947A CN 02156898 CN02156898 CN 02156898 CN 02156898 A CN02156898 A CN 02156898A CN 1413947 A CN1413947 A CN 1413947A
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- China
- Prior art keywords
- gallium oxide
- zinc
- ceramic target
- film
- target
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- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 35
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000011701 zinc Substances 0.000 title claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000011224 oxide ceramic Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title description 4
- 239000013077 target material Substances 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000005477 sputtering target Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000007723 die pressing method Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- 229960001296 zinc oxide Drugs 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910017911 MgIn Inorganic materials 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- Physical Vapour Deposition (AREA)
Abstract
A zinc gallium oxide ceramic target used for sputtering and electrically conductive transparent film is prepared through mixing zinc oxide powder with gallium oxide powder, cold die pressing and sintering. Its advantages are simple process, low cost and high stability of performance. The said film has excellent photoelectric performance, so it can be used as the electrode of solar cell.
Description
Technical field
The invention belongs to the photoelectric material technical field, particularly a kind of zinc gallium oxide ceramic target and technology of preparing and application.
Background technology
Transparent conductive oxide (Transparent Conductive Oxide, abbreviation TCO) film mainly comprises oxide compound and the composite multi-component oxide film material thereof of In, Sn, Sb, Zn and Cd, not only transparent but also performance conduction is able to widespread use because of it for photoelectric characteristic such as have that the forbidden band is wide, visible range optical transmittance height and resistivity are low, transparent conductive oxide film.The main application fields of TCO film has at present: (1) flat pannel display, as liquid-crystal display, plasma display, field emission demonstration, electroluminescent demonstration etc.; (2) hot mirror because transparent conductive oxide film has selection perviousness to light wave (promptly to the transmissivity of visible light and to the reflectivity of infrared light), can be used for the building glass window and plays heat shield effect, to save energy consumption; (3) transparent surface calorifier, as on the glass port of the vehicles such as automobile, aircraft as antifog defrosting glass; (4) transparency electrode of solar cell; (5) exploitation of flexible substrate expands the purposes of TCO film to make flexible luminescent device, plastic liquid crystal indicating meter, Foldable solar energy battery and is used for plastic greenhouse, glass bonding film etc. as lagging material.
At present, people have developed ZnO, SnO
2, and In
2SnO
5, ZnOIn
2O
3, Zn
2SnO
4, Zn
2In
2O
5, CdSb
2O
6, CdIn
2O
4, Cd
2SnO
4, GaInO
3, In
4Sn
3O
12, MgIn
2O
4, FTO polynary transparent oxide film materials such as (SnO:F).Wherein most widely used, the most sophisticated still tin-doped indium oxide (Indium Tin Oxide is called for short ITO).Ito thin film has complicated cube ferrimanganic ore deposit structure, and resistivity is low to reach 10
-4The average light transmissivity is more than 80% in the Ω .cm magnitude, visible spectrum range.Its excellent photoelectric property makes it to become the TCO film with actual application value, is topmost planar transparent electrode materials in the flat-panel display device.The production of present commercial ito thin film mainly is the sputtering method that adopts the ITO ceramic target.The ITO target prepares with the hot isostatic pressing method, its manufacturing process complexity, and equipment and manufacturing cost are higher than its material cost far away.Prepare in the technology of ito thin film at magnetically controlled sputter method, obtain the film of photoelectric properties excellence, its substrate temperature general requirement is about 350 ℃, and this has limited the range of choice of its substrate material to a certain extent, and relatively the substrate material of Shi Heing is glass and stainless steel etc.And on flexible organism substrate, preparing film, underlayer temperature does not generally allow to surpass 200 ℃, so the ito thin film of processability excellence is comparatively difficult on flexible organism substrate.When ito thin film was applied to solar cell as transparency electrode simultaneously, the In in the film can spread in battery material, made the stability of device descend.
Summary of the invention
At the deficiencies in the prior art and defective, the purpose of this invention is to provide a kind of zinc gallium oxide ceramic target and preparation method thereof; Another object of the present invention provides a kind of application of zinc gallium oxide ceramic target.
Technical scheme of the present invention is as follows:
A kind of zinc gallium oxide ceramic target, it is characterized in that: this ceramic target is made up of zinc, gallium oxide, is to be formed through sintering by Zinc oxide powder and gallium oxide powder, and gallium oxide wherein accounts for 2~7% of total mass.
The method of the described zinc gallium oxide of the preparation ceramic target that the present invention proposes, it is characterized in that: this method comprises the steps:
(1) mass percent is that 98~93% Zinc oxide powder and mass percent are that 2~7% gallium oxide powder mixes mutually, with the method press forming of colding pressing;
(2) with the block sintering under normal pressure, normal atmosphere that is shaped, sintering temperature is at 1000 ℃~1700 ℃.
Another technical scheme of the present invention is to use zinc gallium oxide ceramic target provided by the invention to prepare zinc gallium oxide transparent conductive film as sputtering target material.
The present invention compared with prior art has following outstanding advantage:
1. the zinc gallium oxide ceramic target composition that is provided is simple, has characteristics such as high-accuracy property, stability, reliability, and the target size can reach the general dimensions of present sputter production line.
2. the manufacturing process of target is simple, low production cost, and consistency of performance is good.
3. use the film base strong adhesion of the film of this target preparation, long service life.
4. the sputtering technology of zinc gallium oxide film can be used the d.c. sputtering method, has avoided the damage of radio-frequency sputtering to operator.
5. use the structure of the prepared zinc gallium oxide film of target of the present invention to be the hexagonal wurtzite type, its photoelectric properties can be comparable with ITO, and resistivity reaches 10
-4Average light transmissivity in the Ω .cm magnitude, visible spectrum range is more than 84%.
6. use target of the present invention, the underlayer temperature below 150 ℃ also can the obtained performance excellence zinc gallium oxide film, as the resistivity that is deposited on the zinc gallium oxide film on the polyester film that transparent polyester film, polymeric polyisocyanate and common electrician use can reach 8.0 * 10
-4Ω .cm, transmissivity is greater than 84%.
When 7. zinc gallium oxide film is as the transparency electrode of silica-based solar cell, have can be stable in the H plasma neutral advantage.
8. compare with the zinc-oxide film of mixing aluminium, have wideer visible light transmissive scope and more stable photoelectric properties, moisture resistance properties particularly when this makes it be applied in the solar cell as transparency electrode, can improve the stability and the weather resistance of device effectively.
Embodiment
Embodiment 1:
It is even to be with purity that the gallium oxide powder (account for total mass 2.1%) of 99.9% Zinc oxide powder and purity 99.9% is mixed mutually, adopts the method moulding of colding pressing, and pressure is 2.50 * 10
6N.Sinter the block that density is theoretical density 96% at 1560 ℃, make the target that is of a size of 400mm * 200mm * 6mm.Use this target, adopt the sedimentary method of radio-frequency sputtering at mylar depositing zinc oxide gallium transparent conductive film, the thickness of gained film is 30nm, and resistivity is 6.2 * 10
-4Ω .cm, the visible light transmissivity of 550nm are 86%.
Embodiment 2:
It is even to be with purity that the gallium oxide powder (account for total mass 4.6%) of 99.99% Zinc oxide powder and purity 99.99% is mixed mutually, adopts the method moulding of colding pressing, and pressure is 2.50 * 10
6N.Sinter 95% the block that density is theoretical density at 1180 ℃, make the target that is of a size of 400mm * 200mm * 6mm.Use this target and adopt the sedimentary method of magnetically controlled DC sputtering at deposition on glass zinc-gallium oxide transparent conductive film, the thickness of gained film is 30nm, and resistivity is 3.6 * 10
-4Ω .cm, the visible light transmissivity of 550nm are 88%.
Embodiment 3:
With purity is that the gallium oxide powder (account for total mass 6.8%) of 99.99% Zinc oxide powder and purity 99.99% mixes mutually, adopts the method moulding of colding pressing, and pressure is 2.50 * 10
6N.Sinter 97% the block that density is theoretical density at 1680 ℃, make the target that is of a size of 400mm * 200mm * 6mm (length * wide * height).Be bonded to the target of the production line of 1200mm * 200mm * 6mm with three targets with size, use this target, adopt the sedimentary method of magnetically controlled DC sputtering at deposition on glass zinc-gallium oxide transparent conductive film, the thickness of gained film is 110nm, and resistivity is 4.43 * 10
-4Ω .cm, the transmitance of the visible light of 550nm is 87%.
Embodiment 4:
With the zinc-gallium oxide film that the method for embodiment 3 obtains, be 85 ℃ in temperature, relative humidity is that the resistivity rising value is less than 5% before depositing after depositing 1000 hours under 85% the condition, the transmitance of the visible light of 550nm still remains 87%.
Claims (3)
1. zinc gallium oxide ceramic target, it is characterized in that: this ceramic target is made up of zinc, gallium oxide, is to be formed through sintering by Zinc oxide powder and gallium oxide powder, and gallium oxide wherein accounts for 2~7% of total mass.
2. method for preparing zinc gallium oxide ceramic target as claimed in claim 1, it is characterized in that: this method comprises the steps:
(1) be that 93~98% Zinc oxide powder and mass percent are that 2~7% gallium oxide powder mixes mutually with mass percent, with the method press forming of colding pressing;
(2) with the block sintering under normal pressure, normal atmosphere that is shaped, sintering temperature is at 1000 ℃~1700 ℃.
3. utilize zinc gallium oxide ceramic target as claimed in claim 1 to prepare the application of zinc gallium oxide transparent conductive film as sputtering target.
Priority Applications (1)
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---|---|---|---|
CN 02156898 CN1413947A (en) | 2002-12-20 | 2002-12-20 | Zinc gallium oxide ceramic target material and its preparation method and application |
Applications Claiming Priority (1)
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---|---|---|---|
CN 02156898 CN1413947A (en) | 2002-12-20 | 2002-12-20 | Zinc gallium oxide ceramic target material and its preparation method and application |
Publications (1)
Publication Number | Publication Date |
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CN1413947A true CN1413947A (en) | 2003-04-30 |
Family
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101208453B (en) * | 2005-06-28 | 2010-05-19 | 日矿金属株式会社 | Gallium oxide-zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film |
CN101870580A (en) * | 2009-04-22 | 2010-10-27 | 宜兴佰伦光电材料科技有限公司 | ZD(H)O material for transparent conductive film and preparation method thereof |
CN101326304B (en) * | 2005-12-08 | 2011-05-04 | Jx日矿日石金属株式会社 | Gallium oxide/zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film |
CN101397647B (en) * | 2008-11-03 | 2011-08-17 | 清华大学 | Cu-In-Ga-Se or Cu-In-Al-Se solar cell absorption layer target material and preparation method thereof |
CN102187009A (en) * | 2009-05-01 | 2011-09-14 | 株式会社爱发科 | Sintered body for zno-ga2o3 sputtering target and method for producing same |
CN102191466A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院福建物质结构研究所 | Gallium doped zinc oxide target and preparation method of transparent conductive film thereof |
CN102534496A (en) * | 2012-03-13 | 2012-07-04 | 大连理工大学 | High-thermostability transparent conductive film and preparation method and application thereof |
CN101405427B (en) * | 2006-03-17 | 2012-07-18 | Jx日矿日石金属株式会社 | Zinc oxide-based transparent conductor and sputtering target for forming the transparent conductor |
-
2002
- 2002-12-20 CN CN 02156898 patent/CN1413947A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101208453B (en) * | 2005-06-28 | 2010-05-19 | 日矿金属株式会社 | Gallium oxide-zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film |
CN101326304B (en) * | 2005-12-08 | 2011-05-04 | Jx日矿日石金属株式会社 | Gallium oxide/zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film |
CN101405427B (en) * | 2006-03-17 | 2012-07-18 | Jx日矿日石金属株式会社 | Zinc oxide-based transparent conductor and sputtering target for forming the transparent conductor |
CN101397647B (en) * | 2008-11-03 | 2011-08-17 | 清华大学 | Cu-In-Ga-Se or Cu-In-Al-Se solar cell absorption layer target material and preparation method thereof |
CN101870580A (en) * | 2009-04-22 | 2010-10-27 | 宜兴佰伦光电材料科技有限公司 | ZD(H)O material for transparent conductive film and preparation method thereof |
CN102187009A (en) * | 2009-05-01 | 2011-09-14 | 株式会社爱发科 | Sintered body for zno-ga2o3 sputtering target and method for producing same |
CN102191466A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院福建物质结构研究所 | Gallium doped zinc oxide target and preparation method of transparent conductive film thereof |
CN102534496A (en) * | 2012-03-13 | 2012-07-04 | 大连理工大学 | High-thermostability transparent conductive film and preparation method and application thereof |
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