CN100554512C - The method of Nb doped growing n type ZnO transparent conductive film - Google Patents
The method of Nb doped growing n type ZnO transparent conductive film Download PDFInfo
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- CN100554512C CN100554512C CNB2008100612375A CN200810061237A CN100554512C CN 100554512 C CN100554512 C CN 100554512C CN B2008100612375 A CNB2008100612375 A CN B2008100612375A CN 200810061237 A CN200810061237 A CN 200810061237A CN 100554512 C CN100554512 C CN 100554512C
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- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- 238000004549 pulsed laser deposition Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000002679 ablation Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 239000010980 sapphire Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 31
- 238000002360 preparation method Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012789 electroconductive film Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Abstract
What the method for a kind of Nb doped growing n type ZnO transparent conductive film disclosed by the invention adopted is pulsed laser deposition.Target is by high-purity ZnO and Nb
2O
5The ceramic target of powder technique, wherein the molar content of Nb is 0.1%～5%.To mix the ZnO ceramic target of Nb and the substrate that cleaned and put into the growth room of pulsed laser deposition device, the growth room vacuumizes, and at pressure is to grow under the pure oxygen atmosphere of 0.01～1Pa, and growth temperature is 100～600 ℃.The inventive method is simple, and electron density can be by regulating the molar content control of Nb in the target; Doped element can realize high-concentration dopant from target; The n type ZnO transparent conductive film that makes has excellent photoelectric performance, and resistivity is 10
-3～10
-4Ω cm, the visible region transmissivity is more than 85%.
Description
Technical field
The present invention relates to the growth method of transparent conductive film, relate in particular to a kind of method of Nb doped growing n type ZnO transparent conductive film.
Background technology
Transparent conductive film be visible region printing opacity, ultraviolet region by, a kind of function film with low resistivity has a wide range of applications in fields such as liquid-crystal display, solar cells.
Mix an amount of Nb among the ZnO
2O
5, the position with Nb replaces Zn forms alms giver Nb
Zn 3+, can regulate the electric property of ZnO effectively.Because Nb
5+With Zn
2+Ionic radius very approaching, so Nb can not cause the wide variation of lattice parameter to substituting of Zn, when Nb content was not too high, Nb mixed the crystalline structure that can not change ZnO.Therefore, Nb Doped n-type ZnO crystal film is the ideal transparent conductive material.
Present commercial transparent conductive film is still based on expensive ITO, if can the good and cheap n type ZnO transparent conductive film of processability, just can be applied on photoelectric devices such as transparency electrode and thin film transistor.
Summary of the invention
The method that the purpose of this invention is to provide a kind of Nb doped growing n type ZnO transparent conductive film.Nb Doped n-type ZnO transparent conductive film of the present invention, its resistivity is 10
-3～10
-4Ω cm, the visible region transmissivity is more than 85%.
What Nb doped growing n type ZnO transparent conductive film adopted is pulsed laser deposition, comprises the steps:
1) takes by weighing the ZnO of 25～30g purity 〉=99.99% and the Nb of 0.01～1g purity 〉=99.99%
2O
5Powder, ball milling mix, compression moulding, then at 1000～1300 ℃ of sintering temperatures, make the ZnO ceramic target of mixing Nb;
2) will mix the growth room that the ZnO ceramic target of Nb and the substrate that cleaned are put into the pulsed laser deposition device, the distance between target and the substrate is 4～6cm, and growth room's suction is at least to 10
-3Pa, substrate heats to 100～600 ℃, the growth room feeds the oxygen of purity 〉=99.99%, control pressure is 0.01～1Pa, opens laser apparatus, allows laser beam focus on target surface ablation target, form twilight sunset, be deposited on the substrate, make Nb Doped n-type ZnO transparent conductive film, film is cooled to room temperature under oxygen atmosphere.
Above-mentioned substrate is sapphire or quartz or glass.
The beneficial effect that the present invention compared with prior art has:
1) method is simple, and n type doping content can be controlled by the content of regulating Nb in the target;
2) the real-time doping of realization alms giver Nb in ZnO transparent conductive film process of growth;
3) because doped element from target, therefore can realize high-concentration dopant;
4) ZnO transparent conductive film of the present invention is more than 85% in the visible region transmissivity.
Description of drawings
Accompanying drawing is a pulsed laser deposition device synoptic diagram, among the figure: laser apparatus 1, growth room 2, target 3, substrate 4.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated by example.
Embodiment 1
1) takes by weighing the ZnO of 25g purity 〉=99.99% and the Nb of 0.01g purity 〉=99.99%
2O
5Powder, ball milling mix, compression moulding, then at 1000 ℃ of sintering temperatures, make the ZnO ceramic target of mixing Nb;
2) will mix the growth room that the ZnO ceramic target of Nb and the Sapphire Substrate of cleaning are put into the pulsed laser deposition device, the distance between target and the Sapphire Substrate is 4cm, and growth room's suction is at least to 10
-3Pa, substrate heats to 100 ℃, the growth room feeds the oxygen of purity 〉=99.99%, control pressure is 0.01Pa, opens laser apparatus, allows laser beam focus on target surface ablation target, form twilight sunset, be deposited on the substrate, make Nb Doped n-type ZnO transparent conductive film, film is cooled to room temperature under oxygen atmosphere.
Embodiment 2
1) takes by weighing the ZnO of 30g purity 〉=99.99% and the Nb of 1g purity 〉=99.99%
2O
5Powder, ball milling mix, compression moulding, then at 1300 ℃ of sintering temperatures, make the ZnO ceramic target of mixing Nb;
2) will mix the growth room that the ZnO ceramic target of Nb and the quartz substrate of cleaning are put into the pulsed laser deposition device, the distance between target and the quartz substrate is 6cm, and growth room's suction is at least to 10
-3Pa, substrate heats to 600 ℃, the growth room feeds the oxygen of purity 〉=99.99%, control pressure is 1Pa, opens laser apparatus, allows laser beam focus on target surface ablation target, form twilight sunset, be deposited on the substrate, make Nb Doped n-type ZnO transparent conductive film, film is cooled to room temperature under oxygen atmosphere.
Embodiment 3
With glass is the substrate growing n type ZnO transparent electroconductive film, and concrete steps are as follows:
1) to take by weighing 25.4g purity be that 99.99% ZnO and 0.25g purity are 99.99% Nb in the preparation of ceramic target
2O
5Powder.With load weighted ZnO and Nb
2O
5Powder is poured in the ball grinder that agate ball is housed, and ball milling is 48 hours on ball mill, and purpose is with ZnO and Nb
2O
5Powder mixes is also refinement to a certain extent evenly.Then raw material is separated and dried, add binding agent and grind compression moulding.The idiosome of moulding is put into sintering oven, plain through low temperature (400 ℃) row, make the binding agent volatilization, be warming up to 1200 ℃ of sintering again 3 hours, make the Nb molar content and be 0.6% Nb doping ZnO ceramic target.
2) preparation of the film ZnO ceramic target that will mix Nb is contained on the target frame, embeds then in the target holder of pulsed laser deposition device.Glass substrate is fixed on the sample table after cleaning, puts into growth room 2.The distance of regulating substrate 4 and target 3 is 4.5cm, and with baffle plate substrate and target is separated.Growth room's vacuum tightness is evacuated to 8 * 10
-4Pa, substrate are heated to 400 ℃ of film growth temperature.Feed pure O
2, pressure is controlled at 0.03Pa.Open laser apparatus 1 (pulsed laser energy is 200mJ, frequency 3Hz), pre-deposition 10min removes staining of target material surface, the baffle plate of outwarding winding then, deposit film.Substrate and target low speed rotation in the deposition process are to improve the homogeneity of film.Depositing time is 60min, the thick 400nm that is about of film.The growth ending rear film slowly cools to room temperature under the oxygen protection of 5Pa.
The light at room temperature electrical property of above-mentioned Nb Doped n-type ZnO transparent conductive film is good: resistivity is 7.53 * 10
-4Ω cm, electron density is 5.16 * 10
20Cm
-3, hall mobility is 16.1cm
2/ V.s, the visible region projection ratio is greater than 88%, and the photoelectricity performance of placing several months rear film does not have considerable change.
Embodiment 4
The preparation method is with embodiment 1, and difference is that growth substrates is quartzy.The room temperature resistivity of the Nb Doped n-type ZnO transparent conductive film that this example makes is 7.64 * 10
-4Ω cm, electron density is 3.75 * 10
20Cm
-3, hall mobility is 21.7cm
2/ V.s, the visible region projection ratio is greater than 89%, and the photoelectricity performance of placing several months rear film does not have considerable change.
Embodiment 5
The preparation method is with embodiment 1, and difference is that the Nb molar content in the doping ZnO ceramic target is 0.3%.The room temperature resistivity of the Nb Doped n-type ZnO transparent conductive film that this example makes is 1.38 * 10
-3Ω cm, electron density is 2.62 * 10
20Cm
-3, hall mobility is 17.2cm
2/ V.s, the visible region projection ratio is greater than 87%, and the photoelectricity performance of placing several months rear film does not have considerable change.
Claims (2)
1. what the method for a Nb doped growing n type ZnO transparent conductive film adopted is pulsed laser deposition, it is characterized in that comprising the steps:
1) takes by weighing the ZnO of 25～30g purity 〉=99.99% and the Nb of 0.01～1g purity 〉=99.99%
2O
5Powder, ball milling mix, compression moulding, then at 1000～1300 ℃ of sintering temperatures, make the ZnO ceramic target of mixing Nb;
2) will mix the growth room that the ZnO ceramic target of Nb and the substrate that cleaned are put into the pulsed laser deposition device, the distance between target and the substrate is 4～6cm, and growth room's suction is at least to 10
-3Pa, substrate heats to 100～600 ℃, the growth room feeds the oxygen of purity 〉=99.99%, control pressure is 0.01～1Pa, opens laser apparatus, allows laser beam focus on target surface ablation target, form twilight sunset, be deposited on the substrate, make Nb Doped n-type ZnO transparent conductive film, film is cooled to room temperature under oxygen atmosphere.
2. the method for a kind of Nb doped growing n type ZnO transparent conductive film according to claim 1 is characterized in that described substrate is sapphire or quartz or glass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100612375A CN100554512C (en) | 2008-03-18 | 2008-03-18 | The method of Nb doped growing n type ZnO transparent conductive film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100612375A CN100554512C (en) | 2008-03-18 | 2008-03-18 | The method of Nb doped growing n type ZnO transparent conductive film |
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| Publication Number | Publication Date |
|---|---|
| CN101245460A CN101245460A (en) | 2008-08-20 |
| CN100554512C true CN100554512C (en) | 2009-10-28 |
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| CN105040107A (en) * | 2015-06-02 | 2015-11-11 | 济南大学 | Additional electrostatic field assisted semiconductor material doping method |
| CN113651598B (en) * | 2021-08-11 | 2022-06-21 | 芜湖映日科技股份有限公司 | IZO doped target material and preparation method thereof |
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Granted publication date: 20091028 Termination date: 20190318 |