CN101671119A - Method for preparing Li-doped P-type zinc oxide film - Google Patents
Method for preparing Li-doped P-type zinc oxide film Download PDFInfo
- Publication number
- CN101671119A CN101671119A CN200910196556A CN200910196556A CN101671119A CN 101671119 A CN101671119 A CN 101671119A CN 200910196556 A CN200910196556 A CN 200910196556A CN 200910196556 A CN200910196556 A CN 200910196556A CN 101671119 A CN101671119 A CN 101671119A
- Authority
- CN
- China
- Prior art keywords
- film
- zinc
- temperature
- oxide film
- doped
- 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.)
- Pending
Links
Images
Abstract
The invention relates to a method for preparing a Li-doped P-type zinc oxide film, which belongs to the technical field of the preparation technique of a semiconductor electric function film. The invention adopts a sol-gel method to prepare a Li-doped P-type ZnO transparent conductive film. The method mainly comprises the following steps: adopting a potassium-containing organic compound and a zinc-containing organic compound as the precursor, taking an organic solution as a solvent, reacting under stirring at a temperature to generate a colloid, then preparing a ZnO film on a quartz substrateby a spin coating method, carrying out preheating treatment at a certain temperature, and finally removing hydrogen atoms in the film by high-temperature annealing treatment to obtain the stable and transparent P-type ZnO conductive film.
Description
Technical field
The present invention relates to the preparation method of a kind of Li doped P-type zinc-oxide film, belong to semi-conductor electricity function film fabricating technology field.
Background technology
ZnO is a kind of II-VI group iii v compound semiconductor material, energy gap is 3.37eV, exciton binding energy is 60meV under the room temperature, all has excellent performance at photoelectricity, piezoelectricity, thermoelectricity, numerous areas such as ferroelectric, in short-wavelength light electrical part field great application potential is arranged, also show excellence in low-dimensional nanometer field, have various nanostructures.
Be implemented in the widespread use of photoelectric field, at first necessary good n-type and the p-type ZnO material of obtained performance, and realize transparent ZnO Homojeneous p-n Junction.High-quality n-type ZnO is easy to realize that its inherent polarity is but very difficult but the p-type of ZnO mixes, and this is the bottleneck that restricts the ZnO practical application at present, also is the main challenge that faces in the ZnO research.In general, cause that the difficult factor of mixing mainly contains three aspects: the solid solubility of (1) impurity is lower.(2) though impurity has enough solid solubility, very dark impurity level is arranged but, under working temperature, can not be ionized.(3) formation compensating defective that can be spontaneous.First factor mainly depends on the selection and the growing environment of impurity.Second factor only depends on the selection of impurity.Therefore, these two factors can solve by selecting suitable impurity, control growing environment sometimes.The 3rd factor but is semi-conductor intrinsic essential problem, and the most difficult being overcome is particularly for wide bandgap semiconductor.This be because semi-conductor in compensating defective formation can with fermi level (E
F) there is the linear relation that relies on residing position.
After being impregnated in impurity in the semi-conductor, fermi level meeting shift position, this can cause spontaneous formation compensating defective.Such as, mixing when semi-conductor being carried out the p-type, fermi level can move to the direction of top of valence band.So the formation of charged alms giver's defective can will reduce, because they need provide electronics (as shown in Figure 1) in the Fermi pond.Because wide bandgap semiconductor has lower top of valence band, it is very big that the reduction amplitude of alms giver's defective formation energy can become, and this can promote the formation of alms giver's defective greatly.In addition, lower top of valence band position can cause higher acceptor ionization energy.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of Li doped P-type zinc-oxide film
The present invention adopts sol-gel method to prepare the Li doped P-type ZnO transparent conductive film.
The preparation method of a kind of Li doped P of the present invention-type zinc-oxide film is characterized in that having following process and step:
A. adopting analytically pure Zinc diacetate dihydrate is the presoma of ZnO, and Lithium Acetate is a doping agent, is solvent with the ethylene glycol monomethyl ether, with diethanolamine as stablizer; At first take by weighing equimolar Zinc diacetate dihydrate and diethanolamine is dissolved in the certain amount of solvent ethylene glycol monomethyl ether with electronic balance; Stirring makes and mixes; And then add a certain amount of Lithium Acetate; Making the molar mass of lithium ion and the ratio of zine ion molar mass is 0.1: 1; The molar concentration rate that also is Lithium Acetate and zinc acetate solution is 0.1: 1; Gained mixed solution constant temperature under 60 ℃ of temperature was stirred 1～2 hour, obtain clarifying uniform colloidal solution,, obtain colloidal sol this solution left standstill 24～36 hours;
B. then use spin-coating method to film; The above-mentioned colloidal sol that makes is dropped on the silica glass substrate that cleans up, with 30～40 seconds film forming of rotating speed spin coating of 3000rpm; Be put into then in the roasting glue machine and carry out thermal pretreatment, temperature is 300～400 ℃, and the hold-time is 5～10 minutes, with materials such as organism in the removal film and water, and improves adhesion of thin film; Repeat above-mentionedly to be coated with membrane operations repeatedly, obtain the certain thickness Li of mixing zinc-oxide film;
C. and then above-mentioned zinc-oxide film is put into the tubular type annealing furnace carry out The high temperature anneal, treatment temp is to be 2～3 hours between 500～800 ℃, and temperature rise rate is 4～6 ℃/min; Treat that sample is cooled to room temperature, take out, preserve with sealing bag, stand-by; Final product is Li doped P-type zinc-oxide film.
Principle of the present invention and characteristics are as described below:
The Li doping ZnO of sol-gel method preparation is a presoma with the organism, can introduce a large amount of H atoms in preparation process, is present in the unannealed film.The H atom exists with the form of gap or displacement, and these two kinds of forms all are the shallow donors.We know that the formation of compensating defective can have substantial connection with the position of fermi level.When the conduction type that changes ZnO, when carrying out the doping of p-type, fermi level E
FDirection to top of valence band moves (referring to Fig. 1), and the formation of donor-type defective at this moment can reduce.In process of growth, introduce the H atom and can live fermi level by pinning, reduce the formation energy that is subjected to major defects, promote to be subjected to major defects displacement lithium Li
ZnFormation, improve the formation energy of alms giver's defective simultaneously, suppress alms giver's defective gap lithium Li
iGeneration.In addition, some displacement lithium Li
ZnCan be by gap hydrogen H
iWith L
Zn-H
iCompound right form compensates.Except forming L
Zn-H
iCompound external, displacement lithium Li
ZnMeeting and gap lithium Li equally
iForm Li
Zn-Li
iForm compound right.Like this, because a large amount of displacement lithium Li
ZnFallen by compound, the Li doping ZnO does not manifest p-type electroconductibility before not passing through The high temperature anneal, be similar to isolator.When 300 ℃ annealing temperature, Li
Zn-Li
iCompound meeting is broken and gap lithium Li
iCan diffuse out ZnO.And when annealing temperature is higher than 500 ℃, Li
Zn-H
iCompound meeting is broken and gap hydrogen H
iCan go out from ZnO body internal diffusion.Therefore, after annealing temperature reached 500 ℃, ZnO began to demonstrate weak p-type conductive features.When temperature is increased to 600 ℃, can continue to separate most Li
Zn-H
iCompound right, and expulsion H atom.At this moment the p-type electroconductibility of ZnO is obviously improved, and hole concentration also further improves.Certainly, owing to also exist the H atom of displacement attitude, this is a kind of more stable shallow donor's defective, so when annealing temperature arrived 700 ℃, displacement H just can be excluded out ZnO.So behind the compensating action of having eliminated displacement H, sample shows best p-type conduction at 700 ℃, and the highest cavity type carrier concentration is arranged, the hole becomes the majority carrier in the ZnO film.
The inventive method is different from the method that usual vacuum environment prepares film, as methods such as magnetron sputtering or pulsed laser depositions, because be difficult to the hydrogen atom that provides a large amount of under the vacuum environment.And characteristics of the present invention be the organic compound that can select to contain hydrogen atom as starting material, can prepare by the ZnO film of hydrogen atom passivation, get rid of inner hydrogen atom by pyroprocessing subsequently, obtain p-type ZnO film material.
Description of drawings
Fig. 1 for charged defects among the present invention form can with the synoptic diagram that concerns of fermi level position.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment: preparation process and step in the present embodiment are as follows:
(1), adopts analytically pure Zinc diacetate dihydrate (Zn (CH
3COO) 22H
2O)) as the presoma of ZnO, be solvent with the ethylene glycol monomethyl ether, with diethanolamine as stablizer; At first take by weighing equimolar Zinc diacetate dihydrate and diethanolamine is dissolved in it in solvent ethylene glycol methyl ether of a certain amount of 60mL with electronic balance; Add appropriate amount of deionized water, stirring makes and mixes; And then add a certain amount of Lithium Acetate (CH
3COOLi2H
2O); The volumetric molar concentration that makes Lithium Acetate solution is 0.03mol/L, and the volumetric molar concentration of zinc acetate solution is 0.3mol/L, and it is between the two than being 0.1: 1; The mixed solution of gained constant temperature under 60 ℃ of temperature was stirred 1 hour, obtain uniform colloidal solution,, obtain colloidal sol this solution left standstill 24 hours;
(2), then use spin-coating method to film; The above-mentioned colloidal sol that makes is dropped on the silica glass substrate that cleans up, with 30 seconds film forming of rotating speed spin coating of 3000rpm; Be put into then in the roasting glue machine and carry out thermal pretreatment, temperature is 300 ℃, and the hold-time is 5 minutes, with materials such as organism in the removal film and water, and improves adhesion of thin film; Repeat above-mentionedly to be coated with membrane operations 3 times, obtain the certain thickness Li of mixing zinc-oxide film;
(3) and then above-mentioned zinc-oxide film is put into the tubular type annealing furnace carry out The high temperature anneal, treatment temp is to be 2 hours between 700 ℃, and temperature rise rate is 5 ℃/min; Treat that sample is cooled to room temperature, take out, preserve with sealing bag, stand-by; Final product is Li doped P-type zinc-oxide film.
In addition, utilize above-mentioned same quadrat method and step, done some contrast comparison tests, promptly prepared the adulterated zinc oxide films membrane sample of no Li, and the Li doping zinc-oxide film sample of final high temperature anneal after handling under 500～800 ℃ of temperature, and it some performance tests have been carried out.
The test result of each ZnO film sample is listed in the table below in 1:
The test result of this sample of table 1
By table as seen, before the lithium doping, the ZnO sample presents n-type electroconductibility.Behind the lithium doping, through The high temperature anneal, ZnO presents p-type electroconductibility, and under 700 ℃ condition, conductivity is best, and resistivity only is 46.8 Ω cm.
Certainly, the too high meeting of annealing temperature causes the reduction of conductivity.After temperature reached 800 ℃, resistivity obviously increased.This is that cracking phenomena appears in film because excessive temperature can make THERMAL STRESS IN THIN FILMS increase.
Preparation method of the present invention can realize that the p-type of ZnO mixes, and then realizes the preparation of PN homojunction.Preparation method of the present invention is simple, and the lower cost for material of use is extensively abundant, and does not need expensive vacuum apparatus, does not need many high temperature services, just can prepare the p-type ZnO film of excellent property.
Claims (1)
1, the preparation method of a kind of Li doped P-type zinc-oxide film is characterized in that having following process and step:
A. adopting analytically pure Zinc diacetate dihydrate is the presoma of ZnO, and Lithium Acetate is a doping agent, is solvent with the ethylene glycol monomethyl ether, with diethanolamine as stablizer; At first take by weighing equimolar Zinc diacetate dihydrate and diethanolamine is dissolved in the certain amount of solvent ethylene glycol monomethyl ether with electronic balance; Stirring makes and mixes; And then add a certain amount of Lithium Acetate; Making the molar mass of lithium ion and the ratio of zine ion molar mass is 0.1: 1; The molar concentration rate that also is Lithium Acetate and zinc acetate solution is 0.1: 1; Gained mixed solution constant temperature under 60 ℃ of temperature was stirred 1～2 hour, obtain clarifying uniform colloidal solution,, obtain colloidal sol this solution left standstill 24～36 hours;
B. then use spin-coating method to film; The above-mentioned colloidal sol that makes is dropped on the silica glass substrate that cleans up, with 30～40 seconds film forming of rotating speed spin coating of 3000rpm; Be put into then in the roasting glue machine and carry out thermal pretreatment, temperature is 300～400 ℃, and the hold-time is 5～10 minutes, with materials such as organism in the removal film and water, and improves adhesion of thin film; Repeat above-mentionedly to be coated with membrane operations repeatedly, obtain the certain thickness Li of mixing zinc-oxide film;
C. and then above-mentioned zinc-oxide film is put into the tubular type annealing furnace carry out The high temperature anneal, treatment temp is to be 2～3 hours between 500～800 ℃, and temperature rise rate is 4～6 ℃/min; Treat that sample is cooled to room temperature, take out, preserve with sealing bag, stand-by; Final product is Li doped P-type zinc-oxide film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910196556A CN101671119A (en) | 2009-09-27 | 2009-09-27 | Method for preparing Li-doped P-type zinc oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910196556A CN101671119A (en) | 2009-09-27 | 2009-09-27 | Method for preparing Li-doped P-type zinc oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101671119A true CN101671119A (en) | 2010-03-17 |
Family
ID=42018577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910196556A Pending CN101671119A (en) | 2009-09-27 | 2009-09-27 | Method for preparing Li-doped P-type zinc oxide film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101671119A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392237A (en) * | 2011-10-26 | 2012-03-28 | 东北大学 | Preparation method for Ag-Li co-doped zinc oxide film |
| CN102810483A (en) * | 2012-08-07 | 2012-12-05 | 清华大学 | Oxide semiconductor film and preparation method thereof, thin film transistor and preparation method |
| CN103107291A (en) * | 2011-11-11 | 2013-05-15 | 海洋王照明科技股份有限公司 | Substrate of organic electroluminescence device and production method thereof |
| CN103343335A (en) * | 2013-06-08 | 2013-10-09 | 深圳市亚太兴实业有限公司 | Preparation methods for boron-doped zinc oxide film |
| CN103803635A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Preparation method of Li ion-doped ZnO superfine nano rod |
| CN106065493A (en) * | 2016-07-29 | 2016-11-02 | 中山大学 | A kind of high resistivity single-crystal zinc-oxide and its preparation method and application |
| CN106676633A (en) * | 2016-11-15 | 2017-05-17 | 常州大学 | Preparation method of Li-doped ZnO crystal thin film |
| CN108767132A (en) * | 2018-06-15 | 2018-11-06 | 嘉兴纳鼎光电科技有限公司 | The production method of electron transfer layer and light emitting diode with quantum dots device |
| CN108821327A (en) * | 2018-06-27 | 2018-11-16 | 五邑大学 | The preparation method and its application of the pineal ZnO nano microballoon of one type |
| CN112079375A (en) * | 2020-09-04 | 2020-12-15 | 中山大学 | Nitric oxide annealing process and device for removing lithium in zinc oxide gap |
| CN113120949A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Zinc oxide nano material, preparation method thereof, thin film and photoelectric device |
-
2009
- 2009-09-27 CN CN200910196556A patent/CN101671119A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392237A (en) * | 2011-10-26 | 2012-03-28 | 东北大学 | Preparation method for Ag-Li co-doped zinc oxide film |
| CN103107291A (en) * | 2011-11-11 | 2013-05-15 | 海洋王照明科技股份有限公司 | Substrate of organic electroluminescence device and production method thereof |
| CN102810483A (en) * | 2012-08-07 | 2012-12-05 | 清华大学 | Oxide semiconductor film and preparation method thereof, thin film transistor and preparation method |
| CN103343335A (en) * | 2013-06-08 | 2013-10-09 | 深圳市亚太兴实业有限公司 | Preparation methods for boron-doped zinc oxide film |
| CN103343335B (en) * | 2013-06-08 | 2016-03-23 | 徐东 | The preparation method of boron-doping zinc-oxide film |
| CN103803635A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Preparation method of Li ion-doped ZnO superfine nano rod |
| CN106065493A (en) * | 2016-07-29 | 2016-11-02 | 中山大学 | A kind of high resistivity single-crystal zinc-oxide and its preparation method and application |
| CN106676633A (en) * | 2016-11-15 | 2017-05-17 | 常州大学 | Preparation method of Li-doped ZnO crystal thin film |
| CN108767132A (en) * | 2018-06-15 | 2018-11-06 | 嘉兴纳鼎光电科技有限公司 | The production method of electron transfer layer and light emitting diode with quantum dots device |
| CN108821327A (en) * | 2018-06-27 | 2018-11-16 | 五邑大学 | The preparation method and its application of the pineal ZnO nano microballoon of one type |
| CN113120949A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Zinc oxide nano material, preparation method thereof, thin film and photoelectric device |
| CN112079375A (en) * | 2020-09-04 | 2020-12-15 | 中山大学 | Nitric oxide annealing process and device for removing lithium in zinc oxide gap |
| CN112079375B (en) * | 2020-09-04 | 2021-08-20 | 中山大学 | Nitric oxide annealing process and device for removing lithium in zinc oxide gap |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101671119A (en) | Method for preparing Li-doped P-type zinc oxide film | |
| US10109755B2 (en) | Capping layers for improved crystallization | |
| US5112410A (en) | Cadmium zinc sulfide by solution growth | |
| JP2010517291A (en) | Doped nanoparticle semiconductor charge transport layer | |
| CN113078239B (en) | Antimony selenide thin film solar cell and preparation method thereof | |
| CN103531660A (en) | In-doped zinc sulfide thin film and preparation method and application thereof | |
| Saha | A status review on Cu2ZnSn (S, Se) 4-based thin-film solar cells | |
| JP2004015039A (en) | Compound thin film solar cell and method for manufacturing the same | |
| Chu et al. | Semi-transparent thin film solar cells by a solution process | |
| US20170207362A1 (en) | Method for forming thin film having sulfide single-crystal nanoparticles | |
| US20130327377A1 (en) | Thin Film Chalcogenide Photovoltaic Device and Method for Forming the Same | |
| CN110165020B (en) | Based on CdS/SnO2High efficiency Sb of mixed N type layer2Se3Thin film battery and preparation method thereof | |
| KR101558589B1 (en) | Method of fabricating of solar cell | |
| CN105449103A (en) | Thin film crystalline silicon perovskite heterojunction solar cell and preparation method thereof | |
| CN112563118B (en) | In-doped CdS film, preparation method and CIGS cell prepared by same | |
| Munshi et al. | Doping CdSe x Te 1-x/cdte graded absorber films with arsenic for thin-film photovoltaics | |
| CN113054114B (en) | Solar cell based on D-A type organic micromolecule doped ZnO electron transport layer and preparation method thereof | |
| CN104600144A (en) | High-efficiency copper indium gallium selenium thin-film photocell based on bulk heterojunction structure light absorption layer | |
| KR20110001755A (en) | Solar cell and method of fabricating the same | |
| CN108269867A (en) | Compound solar cell and method for manufacturing light absorption layer | |
| CN108807572B (en) | Silver indium gallium selenide thin film and preparation method and application thereof | |
| US9159863B2 (en) | Method of forming chalcopyrite thin film solar cell | |
| CN113161488A (en) | Homogeneous junction charge transmission film for perovskite solar cell | |
| KR101835580B1 (en) | Prepration method of CZTS or CZTSe thin film solar cell using co-evaporation and solar cell prepared by the same | |
| Luo et al. | Recent Progress on Cu2BaSn (SxSe1–x) 4: From Material to Solar Cell Applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100317 |