CN104332540B - A kind of method for preparing high luminescence energy p-type ZnO film - Google Patents
A kind of method for preparing high luminescence energy p-type ZnO film Download PDFInfo
- Publication number
- CN104332540B CN104332540B CN201410618510.5A CN201410618510A CN104332540B CN 104332540 B CN104332540 B CN 104332540B CN 201410618510 A CN201410618510 A CN 201410618510A CN 104332540 B CN104332540 B CN 104332540B
- Authority
- CN
- China
- Prior art keywords
- type zno
- zno film
- sputtering
- film
- pure
- 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.)
- Active
Links
- 238000004020 luminiscence type Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000004544 sputter deposition Methods 0.000 claims abstract description 29
- 239000013528 metallic particle Substances 0.000 claims abstract description 12
- 230000033228 biological regulation Effects 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000004062 sedimentation Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 8
- 230000026267 regulation of growth Effects 0.000 claims description 5
- 230000007547 defect Effects 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 32
- 239000010409 thin film Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- 229910052594 sapphire Inorganic materials 0.000 description 4
- 239000010980 sapphire Substances 0.000 description 4
- 229910003363 ZnMgO Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- -1 growth time is 5 h Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/14—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
The method of high luminescence energy p-type ZnO film disclosed by the invention, step includes：Using molecular beam epitaxial device, by pure O2By the oxygen plasma of rf active formation as O sources, with simple metal Zn sources as reaction source, with the pure NaF powder of solid as p-type doped source, in Grown p-type ZnO film；The p-type ZnO film of acquisition is placed in ion-sputtering system, regulation sputtering current to 10~15 mA, in film surface sputtering sedimentation Pt or Au metallic particles, sputtering time is 20~100 s.The inventive method is simply controllable, while p-type ZnO film band-edge emission is strengthened, restrained effectively defect luminescence, drastically increases the luminescent properties of p-type ZnO, for the zno-based photoelectric device for preparing high luminescence energy is laid a good foundation.
Description
Technical field
The present invention relates to a kind of growing method of p-type ZnO film, especially the preparation side of high luminescence energy p-type ZnO film
Method.
Background technology
ZnO material is up to 60 meV as broad stopband direct band-gap semicondictor material, exciton bind energy, in ultraviolet light photo neck
There is huge application prospect in domain, and the excellent N-shaped of processability and p-type ZnO film are to realize its wide variety of key.Mesh
Before, the N-shaped ZnO film with excellent properties can be obtained.But due to doping asymmetry, it is difficult to obtain the p-type of excellent performance
ZnO, this seriously constrains the development of zno-based photoelectric device.
Have reported the p-type electric-conducting that ZnO film is realized using different doped sources in the world at present, but the film for being obtained lacks
Fall into more, band edge is luminous weaker, defect luminescence substantially, simultaneously because hole mobility is low, causes the Homojeneous p-n Junction of final preparation
Electron-hole recombinations occur mainly in the relatively poor p areas of quality, this greatly limits the luminescent properties of device.In recent years,
Increasing ZnMgO electronic barrier layers turns into the main path for overcoming this problem at present.However, ZnMgO/ZnO heterostructure band knots
Structure is I type structures, and ZnMgO provide not only electron transition potential barrier, Carrier recombination is limited in into active area；Meanwhile, also provide
Hole transition potential barrier, prevents transmission of the partial holes to active area, and this similarly limits the luminescent properties of device.In addition
On the one hand, electronic barrier layer can not fundamentally solve the problems, such as that p-type layer luminescent properties are poor.Therefore, development is needed badly a kind of new
Approach solve this problem.
The content of the invention
Can strengthen luminous and suppression defect luminescence the high luminescence energy p-type ZnO of band edge it is an object of the invention to provide a kind of
The preparation method of film.
The method for preparing high luminescence energy p-type ZnO film of the invention, comprises the following steps：
1）Cleaned substrate is put into molecular beam epitaxial device, underlayer temperature is heated to 400~600 DEG C, will
Pure O2By the oxygen plasma of rf active formation as O sources, growth regulation chamber pressure is 2 × 10-6~8 × 10-6Torr,
With simple metal Zn sources as reaction source, regulation Zn source temperatures are 260~350 DEG C, with the pure NaF powder of solid as p-type doped source, are adjusted
400~620 DEG C of section Na source temperatures, in Grown p-type ZnO film；
2）The p-type ZnO film of acquisition is placed in ion-sputtering system, sputtering current is adjusted to 10~15 mA, thin
Film surface sputtering sedimentation Pt or Au metallic particles, sputtering time is 20~100 s.
In the present invention, described pure O2Purity be 99.9999 more than %, the purity of simple metal Zn for 99.9998 % with
On, the purity of pure NaF powder is 99.995 more than %.
In the present invention, described substrate can be ZnO bodies monocrystalline or a surface sapphires or c surface sapphires or m surface sapphires.
The present invention sputters the sputtering time and sputtering current of Pt or Au metallic particles by adjusting, thus it is possible to vary p-type ZnO is thin
The luminescent properties of film.
The beneficial effects of the present invention are：
The present invention is using in metallic particles such as p-type ZnO film surface sputtering sedimentation Pt, Au, on the one hand, metallic particles with
The interface of film produces metallic surface plasma excimer, and the resonance coupling lighted using surface plasmons and band edge is made
With the band-edge emission of enhancing p-type ZnO film；On the other hand, due to the Fermi levels such as Pt, Au and the defect level of ZnO
Match somebody with somebody, the electronics in defect level can easily be transferred to metallic particles, so as to restrained effectively the defect luminescence of p-type ZnO.
The inventive method is simply controllable, while p-type ZnO film band-edge emission is strengthened, restrained effectively defect luminescence, greatly
The luminescent properties of p-type ZnO are improve, for the zno-based photoelectric device for preparing high luminescence energy is laid a good foundation.
Brief description of the drawings
Fig. 1 is the Photoluminescence before and after p-type ZnO film sputtering Pt metallic particles.
Specific embodiment
Embodiment 1
1）Molecular beam epitaxial device is put into after m surface sapphire substrates are carried out into cleaning treatment, underlayer temperature is heated to 600
DEG C, growth regulation chamber pressure is 2 × 10-6Torr, with by the pure O of rf active2（The % of purity 99.9999）It is O sources, activation
O2Radio-frequency power be 350 W；Metal Zn（The % of purity 99.9998）Source is reaction source, and regulation Zn source heating-up temperatures are to 280 DEG C；
Solid NaF powder（The % of purity 99.995）It is Na sources, 600 DEG C of regulation Na sources heating-up temperature, growth Na mixes on m surface sapphires
Miscellaneous p-type ZnO film, growth time is 5 h, and film is thick to be about 300 nm.
2）By step 1）The p-type ZnO film of preparation is placed in ion-sputtering system, sputtering current is adjusted to 12mA, thin
Film surface sputtering sedimentation Pt metallic particles, sputtering time is 60 s.
Step 1）Obtained Na doped p type ZnO thin films have excellent room temperature electric property, and resistivity is 510.5 Ω
Cm, hole concentration is up to 2.4 × 1016 cm-3, hall mobility is 0.5 cm2/V·s。
Fig. 1 is shown through step 2）The Photoluminescence of before processing rear film, as seen from the figure, does not sputter Pt particles
Before, film band edge peak is weaker, and defect peak is obvious, thin-film light emitting poor-performing；After sputtering 60 s Pt metallic particles, film
Band edge peak is remarkably reinforced, and does not observe defect peak, nearly 10 times or so of band edge luminescence enhancement, shows to sputter the rear film of Pt particles
With good optical property.
Embodiment 2
1）Molecular beam epitaxial device is put into after m surface sapphire substrates are carried out into cleaning treatment, underlayer temperature is heated to 600
DEG C, growth regulation chamber pressure is 3 × 10-6Torr, with by the pure O of rf active2（Purity 99.9999%）It is O sources, activates O2
Radio-frequency power be 350 W；Metal Zn（The % of purity 99.9998）Source is reaction source, 280 DEG C of regulation Zn sources heating-up temperature；Solid
NaF powder（The % of purity 99.995）It is Na sources, 610 DEG C of regulation Na sources heating-up temperature, growth Na mixes in m surface sapphire substrates
Miscellaneous p-type ZnO film, growth time is 5h, and film is thick to be about 300 nm.
2）By step 1）The p-type ZnO film of preparation is placed in ion-sputtering system, sputtering current is adjusted to 15 mA, thin
Film surface sputtering sedimentation Au metallic particles, sputtering time is 80 s.
Step 1）Obtained Na doped p type ZnO thin films have excellent room temperature electric property, and resistivity is 523.9 Ω
Cm, hole concentration is up to 2.4 × 1016 cm-3, hall mobility is 0.5 cm2/V·s。
Through step 2）The band edge peak for processing rear film is remarkably reinforced, and does not observe defect peak, band edge luminescence enhancement nearly 8
Times.
Embodiment 3
1）Molecular beam epitaxial device is put into after c surface sapphire substrates are carried out into cleaning treatment, underlayer temperature is heated to 500
DEG C, growth regulation chamber pressure is 6 × 10-6Torr, with by the pure O of rf active2（Purity 99.9999%）It is O sources, activates O2
Radio-frequency power be 350 W；Metal Zn（The % of purity 99.9998）Source is reaction source, 300 DEG C of regulation Zn sources heating-up temperature；Solid
NaF powder（The % of purity 99.995）It is Na sources, 500 DEG C of regulation Na sources heating-up temperature grows Na doped p types on c surface sapphires
ZnO film, growth time is 3 h, and film is thick to be about 250 nm.
2）By step 1）The p-type ZnO film of preparation is placed in ion-sputtering system, sputtering current is adjusted to 10 mA, thin
Film surface sputtering sedimentation Pt metallic particles, sputtering time is 50 s.
Step 1）Obtained Na doped p type ZnO thin films have excellent room temperature electric property, and resistivity is 372.0 Ω
Cm, hole concentration is up to 4.2 × 1016 cm-3, hall mobility is 0.4 cm2/V·s。
Through step 2）The band edge peak for processing rear film is remarkably reinforced, and does not observe defect peak, band edge luminescence enhancement nearly 15
Times.
Claims (3)
1. the method for preparing high luminescence energy p-type ZnO film, its step is as follows：
1）Cleaned substrate is put into molecular beam epitaxial device, underlayer temperature is heated to 400~600 DEG C, by pure O2
By the oxygen plasma of rf active formation as O sources, growth regulation chamber pressure is 2 × 10-6~8 × 10-6Torr, with pure
Metal Zn sources are reaction source, and regulation Zn source temperatures are 260~350 DEG C, with the pure NaF powder of solid as p-type doped source, adjust Na
400~620 DEG C of source temperature, in Grown p-type ZnO film；
2）The p-type ZnO film of acquisition is placed in ion-sputtering system, sputtering current is adjusted to 10~15 mA, in film table
Face sputtering sedimentation Pt or Au metallic particles, sputtering time is 20~100 s.
2. the method for preparing high luminescence energy p-type ZnO film according to claim 1, it is characterized in that described substrate is
ZnO bodies monocrystalline or a surface sapphires or c surface sapphires or m surface sapphires.
3. the method for preparing high luminescence energy p-type ZnO film according to claim 1, it is characterized in that described pure O2's
Purity is 99.9999 more than %, and the purity of metal Zn is 99.9998 more than %, and the purity of NaF is 99.995 more than %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410618510.5A CN104332540B (en) | 2014-11-06 | 2014-11-06 | A kind of method for preparing high luminescence energy p-type ZnO film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410618510.5A CN104332540B (en) | 2014-11-06 | 2014-11-06 | A kind of method for preparing high luminescence energy p-type ZnO film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104332540A CN104332540A (en) | 2015-02-04 |
| CN104332540B true CN104332540B (en) | 2017-06-23 |
Family
ID=52407231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410618510.5A Active CN104332540B (en) | 2014-11-06 | 2014-11-06 | A kind of method for preparing high luminescence energy p-type ZnO film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104332540B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106129191A (en) * | 2016-06-29 | 2016-11-16 | 中山大学 | High brightness ultraviolet LED based on Be supplementary doping technology and preparation method thereof |
| CN111128683B (en) * | 2019-12-30 | 2022-07-05 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing P-type zinc oxide film by using molecular beam epitaxy technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101710605A (en) * | 2009-11-26 | 2010-05-19 | 武汉大学 | Ultraviolet light-emitting diode based on n-ZnO/n-GaN alloplasm nN node and preparation method thereof |
| CN102534767A (en) * | 2011-12-29 | 2012-07-04 | 浙江大学 | Na-mixing method for growing p-type ZnO single crystal film |
| CN103031597A (en) * | 2012-12-25 | 2013-04-10 | 浙江大学 | Na-Be codoped p-ZnO film growth method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5502360B2 (en) * | 2009-04-10 | 2014-05-28 | スタンレー電気株式会社 | Zinc oxide based semiconductor device and method for manufacturing the same |
-
2014
- 2014-11-06 CN CN201410618510.5A patent/CN104332540B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101710605A (en) * | 2009-11-26 | 2010-05-19 | 武汉大学 | Ultraviolet light-emitting diode based on n-ZnO/n-GaN alloplasm nN node and preparation method thereof |
| CN102534767A (en) * | 2011-12-29 | 2012-07-04 | 浙江大学 | Na-mixing method for growing p-type ZnO single crystal film |
| CN103031597A (en) * | 2012-12-25 | 2013-04-10 | 浙江大学 | Na-Be codoped p-ZnO film growth method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104332540A (en) | 2015-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Development of pulsed laser deposition for CdS/CdTe thin film solar cells | |
| CN102394263A (en) | Method for enhancing electroluminescent property of n-ZnO/AlN/p-GaN light-emitting diode | |
| CN107293622B (en) | Epitaxial wafer of light emitting diode and preparation method thereof | |
| Zhao et al. | Electroluminescence of the p-ZnO: As/n-ZnO LEDs grown on ITO glass coated with GaAs interlayer | |
| KR20150051181A (en) | PREPARATION METHOD OF CZTSSe-BASED THIN FILM SOLAR CELL AND CZTSSe-BASED THIN FILM SOLAR CELL PREPARED BY THE METHOD | |
| Wang et al. | Ultraviolet electroluminescence properties from devices based on n-ZnO/i-NiO/p-Si light-emitting diode | |
| CN104332540B (en) | A kind of method for preparing high luminescence energy p-type ZnO film | |
| CN108281514A (en) | A kind of preparation method of LED epitaxial slice | |
| CN101685776B (en) | Method for improving ohmic contact of ZnO film | |
| CN103618037B (en) | Doped silicon quantum dot light emitting diode device and preparation method thereof | |
| CN105720148B (en) | Cu doping ZnO is that the ZnO GaN of active layer combine ultra-violet light-emitting pipe and preparation method thereof | |
| JP2010192690A (en) | Method of manufacturing solar cell | |
| CN103474333A (en) | Doping method for p-type zinc telluride single crystal thin-film material | |
| CN107706278B (en) | Preparation method and application of transparent electrode of ultraviolet light-emitting diode | |
| CN110993752A (en) | LED epitaxial growth method taking graphene as buffer layer | |
| CN104451867B (en) | A kind of method for preparing high quality ZnMgBeO films | |
| KR102090184B1 (en) | Solar cell including CIGS light absorbing layer and manufacturing method thereof | |
| CN107681028B (en) | ZnO-based LED chip with vertical structure and preparation method thereof | |
| CN107731971A (en) | A kind of light emitting diode (LED) chip with vertical structure based on photonic crystal and preparation method thereof | |
| CN100449810C (en) | Silicon based MgxZn1-xO ultraviolet electroluminescent device and method for producing the same | |
| CN207938614U (en) | A kind of p-AlN/i-AlN/n-ZnO structures | |
| CN102185071A (en) | Non-polar ZnO-based luminescent device and manufacturing method thereof | |
| CN105336820A (en) | Preparation method of ultraviolet and visible coexisting electroluminescent device | |
| CN101692751B (en) | Device structure for realizing ZnO film pure ultraviolet electroluminescence on p-type silicon | |
| CN102610724B (en) | Electroluminescent device based on CdZnO thin film and preparation method of electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |