CN1388567A - Sol-gel process of preparing p-type ZnO film - Google Patents
Sol-gel process of preparing p-type ZnO film Download PDFInfo
- Publication number
- CN1388567A CN1388567A CN02113083.3A CN02113083A CN1388567A CN 1388567 A CN1388567 A CN 1388567A CN 02113083 A CN02113083 A CN 02113083A CN 1388567 A CN1388567 A CN 1388567A
- Authority
- CN
- China
- Prior art keywords
- sol
- gel
- film
- zno film
- type zno
- 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
- 238000003980 solgel method Methods 0.000 title abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 9
- 239000000084 colloidal system Substances 0.000 abstract 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 61
- 239000011787 zinc oxide Substances 0.000 description 31
- 239000010408 film Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
The sol-gel process of preparing p-type ZnO film includes preparing Ga or N doped ZnO colloid solution, dropping the colloid solution to cleaned Si chip or other substrate, rotating the substrate to make the colloid solution homogeneous, setting the film at the temperature of RM-100 deg.c for a period of time, heat treatment at 240-300 deg.c and heat treatment at 500-900 deg.c in ammonia atmosphere. The preparing process is simple anad low in cost, and can obtain great area film.
Description
One, technical field
The present invention relates to a kind of acquisition p type zinc oxide (ZnO) growth for Thin Film method, mainly is to adopt sol-gel process also
In conjunction with codope method (as Ga and N codope) preparation p type ZnO film.
Two, background technology
ZnO is a very important representative materials of II-VI family composite semiconductor material, has the performance of many excellences, is the preferred material that develops visible-ultraviolet band light emission, optical detection, piezoelectricity and power electronic device.Compare with the sharp GaN of ZnSe, except high direct band gap (3.37eV), it also has following advantage: (1) has very big exciton bind energy (60mev), it is the twice of GaN, even at room temperature, exciton is dominate in its optical property still, thereby has high ultraviolet light emission and more low-energy optical pumping under the room temperature; (2) has the intrinsic backing material; (3) can carry out wet chemistry method handles; (4) has the ability of better Antiradiation injury.In addition, the band edge of ZnO is transmitted in the ultra-violet (UV) band, will be the beginning material that is suitable for very much as white light LEDs.Therefore, ZnO has very important application aspect blue light and ultraviolet optical device even the white light LEDs, thereby causes researcher's attention.
The practical application device major part of ZnO all is based on the ZnO material of polycrystalline or amorphous at present.But in the application aspect the photoelectron, must be high-quality single crystal ZnO material for ZnO.Therefore, growing n-type or the p type electricity high quality ZnO film of leading is necessary.Unfortunately, ZnO has single polarity, and n section bar material is easy to growth in situ and obtains, and p section bar material is difficult to obtain, thereby is difficult to obtain the homogeneity contact of p-n junction.Obtained partly progress for the research work of p-ZnO, as adopting that N or Ga-N mix up etc.But adopt NH
3Decomposition is carried out N and is mixed up, and has repeatable poor, the sharp low carrier concentration (about 1 * 10 of high impedance (100 Ω cm)
16Cm
-3) etc. shortcoming, limited its application further.Theoretical Calculation shows, alms giver among the ZnO (Ga) and mixed up altogether by the doping agent of main (N) can to obtain p-ZnO, and impedance is reduced to 2 Ω cm, and carrier concentration reaches 4 * 10
19Cm
-3This may be because the introducing of Ga has formed the N-Ga-N key, thereby has stablized the N that mixes up among the ZnO.
Preparation at ZnO film, mainly contain following several method at present: laser molecular beam epitaxy (MBE), metal organic vapor phase epitaxy (MOCVD), microwave magnetron sputtering (RF magnetron sputtering) and pulsed laser deposition (PLD) and spraying high temperature pyrolysis (spray pyrolysis) and sol-gel (Sol-Gel) method etc.Prepared by Sol Gel Method ZnO is with traditional laser MBE, MOCVD, the microwave magnetron sputtering is compared with methods such as pulsed laser depositions, it is simple to have method, need not vacuum equipment, be expected preparation large tracts of land ZnO film and the complicated zno-based film of forming on various substrates.
Three, summary of the invention
The present invention seeks to: adopt sol-gel process and prepare p type ZnO film in conjunction with codope method (as Ga and N codope).
Technical solution of the present invention is:
The ZnO colloidal solution for preparing Ga or N codope earlier.Go up the above-mentioned colloidal solution of dropping at cleaned in advance Si sheet or other substrates (quartz glass, sapphire etc.), colloidal solution is evenly applied in the mode of rotating substrate.Then film is placed a period of time in room temperature～100 ℃ down again through Overheating Treatment.Repeat above step several times, obtain the ZnO film of different-thickness.Thereafter at 500～900 ℃, heat treatment is 1～5 hour under the ammonia atmosphere.
Finally, obtained the ZnO film of high-quality c axle orientation, and realized that successfully the P type of ZnO mixes.Mobility is about 10
-2Cm
2/ Vs magnitude, carrier density is 10
16～10
18/ cm
3
Mechanism of the present invention and technical characterstic are:
Sol-gel process prepares thin-film material and possesses skills simply, and low cost is easy to obtain advantages such as large-area film.Because colloidal sol obtains by solution, chemical composition is just the same in the micelle and between micelle, can make multicomponent homogeneous mixture (uniformity coefficient can reach the molecular level level), and can make some and be difficult to obtain with conventional method or unavailable at all product.In the present invention, sol-gal process is evenly distributed in the ZnO crystal grain Ga ion.Ammonia atmosphere is annealing down, forms the N-Ga-N key in ZnO:Ga, N is stabilized in the ZnO lattice and forms p and mix.
Four, embodiment
Concrete steps are as follows:
1, preparation ZnO colloidal solution.Pure zinc acetate of a certain amount of analysis and gallium nitrate are dissolved in the absolute ethyl alcohol, evenly
Stir, and drip till an amount of lactic acid to solution will occur before the precipitation.Continue to stir 2 hours.Final
To ZnO colloidal solution.Wherein, Ga/Zn atomic concentration ratio is 0.05%～10%.
2, go up 0.02ml of dropping at cleaned in advance Si sheet or other substrates (quartz glass, sapphire etc.)
Above-mentioned colloidal solution, evenly be coated on the Si sheet with 2000～3000 revolutions per seconds speed.
3, film was placed 10 minutes to 30 minutes down in room temperature～100 ℃, then at 240～300 ℃ of heat treatment 5-10
Minute.
4, repeat above step 2 and 3 for several times, obtain the ZnO film of different-thickness.
5, at 500～900 ℃, heat treatment is 1～5 hour under the ammonia atmosphere.
Finally, obtained the ZnO film of high-quality c axle orientation, and realized that successfully the P type of ZnO mixes.Mobility is about 10
-2Cm
2/ Vs magnitude, carrier density is 10
16～10
18/ cm
3, resistivity is several approximately to tens Ω cm.
Claims (5)
1, utilize sol-gel (Sol-Gel) legal system to be equipped with p type ZnO film, it is characterized in that preparing earlier the ZnO colloidal solution of Ga or N codope, go up dropping colloidal solution at cleaned in advance Si sheet or other substrates (quartz glass, sapphire etc.), mode with the rotation substrate evenly applies colloidal solution, then film is placed an a period of time in room temperature～100 ℃ down and pass through 240-300 ℃ heat treatment again, thereafter at 500～900 ℃, heat treatment is 1～5 hour under the ammonia atmosphere.
2, be equipped with p type ZnO film by described sol-gel (Sol-Gel) legal system of utilizing of claim 1, it is characterized in that the above step several times of repetition, obtain the ZnO film of different-thickness, at last at 500～900 ℃, heat treatment is 1～5 hour under the ammonia atmosphere.
3, be equipped with p type ZnO film by described sol-gel (Sol-Gel) legal system of utilizing of claim 1, it is characterized in that the atomic concentration ratio of Ga/Zn is 0.05%～10%.
4, be equipped with p type ZnO film by described sol-gel (Sol-Gel) legal system of utilizing of claim 1, it is characterized in that the speed with 2000～3000 revolutions per seconds evenly is coated on the Si sheet.
5, will be equipped with p type ZnO film by described sol-gel (Sol-Gel) legal system of utilizing of claim 1, it is characterized in that film placed 10 minutes to 30 minutes down in room temperature～100 ℃, then at 240～300 ℃ of heat treatment 5-10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021130833A CN1172353C (en) | 2002-05-31 | 2002-05-31 | Sol-gel process of preparing p-type ZnO film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021130833A CN1172353C (en) | 2002-05-31 | 2002-05-31 | Sol-gel process of preparing p-type ZnO film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1388567A true CN1388567A (en) | 2003-01-01 |
| CN1172353C CN1172353C (en) | 2004-10-20 |
Family
ID=4742428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021130833A Expired - Fee Related CN1172353C (en) | 2002-05-31 | 2002-05-31 | Sol-gel process of preparing p-type ZnO film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1172353C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100463859C (en) * | 2007-02-13 | 2009-02-25 | 天津大学 | Preparation process of vertically growing zinc oxide film |
| CN100540756C (en) * | 2007-10-18 | 2009-09-16 | 中国科学院长春光学精密机械与物理研究所 | The method for preparing p type zinc-oxide film with n type zinc oxide |
| CN101118860B (en) * | 2006-08-02 | 2012-07-04 | 施乐公司 | Fabricating zinc oxide semiconductor using hydrolysis |
| CN102557476A (en) * | 2012-01-04 | 2012-07-11 | 上海大学 | Method for preparing gallium-doped zinc oxide film by sol-gel method |
| CN102651432A (en) * | 2012-05-17 | 2012-08-29 | 上海大学 | Method for preparing thin film type LED |
| CN103964702A (en) * | 2014-04-02 | 2014-08-06 | 芜湖浙鑫新能源有限公司 | Preparation method of liquid oxidation film |
| CN106229384A (en) * | 2016-09-14 | 2016-12-14 | 绍兴文理学院 | A kind of preparation method of N doping superlattices metal-oxide film material |
| CN109970356A (en) * | 2017-12-28 | 2019-07-05 | Tcl集团股份有限公司 | Nano zinc oxide material and preparation method thereof, luminescent device |
| CN110752300A (en) * | 2018-07-24 | 2020-02-04 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN110957205A (en) * | 2018-09-27 | 2020-04-03 | 武汉大学苏州研究院 | Preparation method of ohmic contact transparent electrode on p-type GaN |
-
2002
- 2002-05-31 CN CNB021130833A patent/CN1172353C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101118860B (en) * | 2006-08-02 | 2012-07-04 | 施乐公司 | Fabricating zinc oxide semiconductor using hydrolysis |
| CN100463859C (en) * | 2007-02-13 | 2009-02-25 | 天津大学 | Preparation process of vertically growing zinc oxide film |
| CN100540756C (en) * | 2007-10-18 | 2009-09-16 | 中国科学院长春光学精密机械与物理研究所 | The method for preparing p type zinc-oxide film with n type zinc oxide |
| CN102557476B (en) * | 2012-01-04 | 2014-10-15 | 上海大学 | Method for preparing gallium-doped zinc oxide film by sol-gel method |
| CN102557476A (en) * | 2012-01-04 | 2012-07-11 | 上海大学 | Method for preparing gallium-doped zinc oxide film by sol-gel method |
| CN102651432A (en) * | 2012-05-17 | 2012-08-29 | 上海大学 | Method for preparing thin film type LED |
| CN103964702A (en) * | 2014-04-02 | 2014-08-06 | 芜湖浙鑫新能源有限公司 | Preparation method of liquid oxidation film |
| CN106229384A (en) * | 2016-09-14 | 2016-12-14 | 绍兴文理学院 | A kind of preparation method of N doping superlattices metal-oxide film material |
| CN106229384B (en) * | 2016-09-14 | 2017-07-14 | 绍兴文理学院 | A kind of preparation method of N doping superlattices metal-oxide film material |
| CN109970356A (en) * | 2017-12-28 | 2019-07-05 | Tcl集团股份有限公司 | Nano zinc oxide material and preparation method thereof, luminescent device |
| CN109970356B (en) * | 2017-12-28 | 2020-09-25 | Tcl科技集团股份有限公司 | Zinc oxide nano material, preparation method thereof and luminescent device |
| CN110752300A (en) * | 2018-07-24 | 2020-02-04 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN110957205A (en) * | 2018-09-27 | 2020-04-03 | 武汉大学苏州研究院 | Preparation method of ohmic contact transparent electrode on p-type GaN |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1172353C (en) | 2004-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1489654B1 (en) | METHOD OF MANUFACTURING LnCuO(S, Se, Te) MONOCRYSTALLINE THIN FILM | |
| Kim et al. | Optical and structural properties of sputtered CdS films for thin film solar cell applications | |
| Sofiani et al. | Optical properties of ZnO and ZnO: Ce layers grown by spray pyrolysis | |
| CN100555687C (en) | Semiconductor light-emitting elements and manufacture method thereof | |
| CN1172353C (en) | Sol-gel process of preparing p-type ZnO film | |
| Nair et al. | Prospects of chemically deposited CdS thin films in solar cell applications | |
| Bougnot et al. | Chemical spray pyrolysis of CuInSe2 thin films | |
| Wei et al. | β-Ga2O3 thin film grown on sapphire substrate by plasma-assisted molecular beam epitaxy | |
| CN100424233C (en) | Prepn process of polycrystalline Zinc oxide film material | |
| CN1186786C (en) | Diluted magnetic ZnO-base semiconductor prepared by sol-gel method | |
| Zaiour et al. | Impact of deposition methods and doping on structural, optical and electrical properties of ZnO-Al thin films | |
| JP2002105625A (en) | Method for manufacturing low resistivity p-type zinc oxide thin film | |
| Wessler et al. | Textured ZnO thin films on (0001) sapphire produced by chemical solution deposition | |
| CN100365159C (en) | Method for preparing P-zinc oxide film by ion beam intensifying deposition | |
| CN1291453C (en) | N and In codoping process in preparing hole type zinc oxide film | |
| CN1707752A (en) | Spray pyrolyzation processing method for nitride mixing hole type zinc oxide thin film material | |
| CN103103479B (en) | Method for preparing p-type zinc oxide film through sulfur and nitrogen co-doping | |
| CN1258804C (en) | Method for growing p type zinc oxide crystal film by real-time nitrogen doping | |
| CN102746025B (en) | Preparation method of low-cost GaN epitaxial film | |
| CN100437908C (en) | Process for preparing nitrigen-aluminium co-blended hole zinc oxide thin film material | |
| Pirposhte et al. | ZnO Thin Films: Fabrication Routes, and Applications | |
| CN101022141A (en) | Method for producing Mg Sb codoped p type Zno thin film | |
| CN110957205B (en) | Preparation method of ohmic contact transparent electrode on p-type GaN | |
| CN2793100Y (en) | Organic chemical vapor-phase depositor with low-pressure metal for zinc oxide | |
| JPH09153456A (en) | Polycrystalline silicon laminate, thin-film silicon solar cell, and thin-film transistor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |