CN103866280A - Method for preparing donor-acceptor co-doped zinc oxide film by atomic layer deposition - Google Patents
Method for preparing donor-acceptor co-doped zinc oxide film by atomic layer deposition Download PDFInfo
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- CN103866280A CN103866280A CN201210533506.XA CN201210533506A CN103866280A CN 103866280 A CN103866280 A CN 103866280A CN 201210533506 A CN201210533506 A CN 201210533506A CN 103866280 A CN103866280 A CN 103866280A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000000231 atomic layer deposition Methods 0.000 title abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000008021 deposition Effects 0.000 claims abstract description 53
- 239000011701 zinc Substances 0.000 claims abstract description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 229960001296 zinc oxide Drugs 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 230000002000 scavenging effect Effects 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 238000005273 aeration Methods 0.000 claims 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical group FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- 229910015900 BF3 Inorganic materials 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- -1 alkane acid amides Chemical class 0.000 claims 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims 1
- 150000004678 hydrides Chemical class 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 claims 1
- 229910052594 sapphire Inorganic materials 0.000 claims 1
- 239000010980 sapphire Substances 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims 1
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 claims 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 41
- 239000002019 doping agent Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 229910018509 Al—N Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910007744 Zr—N Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a method for preparing a donor-acceptor co-doped zinc oxide film by atomic layer deposition, which comprises the steps of putting a substrate into an ALD reaction chamber, heating the substrate and a chamber pipeline, and then sequentially carrying out multi-component composite deposition; the composite deposition comprises the steps of introducing doping deposition of a donor doping source containing a III main group element X, zinc source deposition for the second time, nitrogen doping source deposition for at least two times and oxygen source deposition for at least two times respectively after zinc source deposition for the first time to form N-X-N codoping; the deposition sequence of the nitrogen doping source and the oxygen source is that the nitrogen doping source is deposited firstly, and then the oxygen source is deposited; the order of deposition of the donor dopant source containing a group III element and the second deposition of the zinc source is first deposition of the donor dopant source containing a group III element and then deposition of the zinc source. The method can carry out in-situ donor-acceptor co-doping on the zinc oxide film so as to increase the doping amount of acceptor elements and promote the p-type conversion of the zinc oxide film.
Description
Technical field
The present invention relates to the preparing technical field of zinc-oxide film, the method that particularly ald is prepared donor-acceptor and mixed altogether zinc-oxide film.
Background technology
Semiconductor film has been given play to very important effect in the new high-tech industries such as microelectronics, optics, information science, preparation and the doping techniques of development high-crystal quality semiconductor film, particularly for preparation, the sign of third generation semiconductor material ZnO film, extremely characteristic research adulterates, for comprising ultraviolet band luminescent material, ultraviolet detector, high integration photonics and electronics device, solar cell etc. are of great significance towards the important applied field tool of new forms of energy.Zinc oxide, as a kind of novel II-VI family direct band gap high-gap compound, have large room temperature energy gap 3.37eV, and free exciton is in conjunction with, up to 60meV, being more and more subject to people's attention as semiconductor material.Compared with other semiconductor material with wide forbidden band, ZnO film growth temperature is low, radioresistance is good, stimulated radiation has lower threshold power and very high effciency of energy transfer, these advantages make ZnO just becoming the new and high technologies such as photoelectron, microelectronics, information after 12, rely continue development key foundation material.But intrinsic ZnO is owing to existing defect, makes ZnO be N-shaped, the preparation of p-type ZnO film is focus and the difficult point of current ZnO correlative study.Although the calculating that nitrogen adulterates in theory makes the preparation of p-type ZnO become possibility, numerous experiments show, because N element solid solubility in ZnO is lower, therefore independent N element doping can not be realized the p-type ZnO film of high carrier concentration and high mobility.In order to address this problem, mixing altogether of acceptor-donor-acceptor is considered to one of direction of preparing the optimum development prospect of high-quality p-ZnO film.
In recent years, the method for making ZnO film generally includes: as magnetron sputtering, metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD) and wet-chemical deposition etc.These preparation technologies respectively have relative merits, better with MOCVD and the standby film quality of MBE legal system from crystallization situation.But the gentle flow point cloth of turbulent flow that MOCVD can not carry out existing in the doping of film and reaction in position can affect thickness and the homogeneity of film.MBE technology is also difficult to realize for the accurate doping of specific atoms layer position.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of the mixing altogether of donor-acceptor that can carry out to zinc-oxide film original position, to increase the incorporation of recipient element, the method that the ald that the p-type of accelerating oxidation zinc film changes is prepared donor-acceptor and mixed altogether zinc-oxide film.
For solving the problems of the technologies described above, the invention provides a kind of method that ald is prepared donor-acceptor and mixed altogether zinc-oxide film, comprising:
Substrate is put into ALD reaction chamber, substrate and chamber tube are heated, then carry out successively multi-component composite deposition;
Described composite deposition is included in for the first time after the deposition of zinc source, introduces respectively the doping deposition in the donor doping source that once comprises III main group element X, zinc source deposition, at least twice nitrogen doping source deposition and at least twice oxygen source deposition for the second time, forms mixing altogether of N-X-N; The sedimentary sequence of described nitrogen doping source deposition and described oxygen source is first nitrogen doping source deposition, rear oxygen source deposition; The described III of comprising main group element donor doping source deposition is first to comprise III main group element donor doping source deposition with described zinc for the second time source sedimentary sequence, after zinc source deposition for the second time.
The method that ald provided by the invention is prepared donor-acceptor and mixed altogether zinc-oxide film, adopt Atomic layer deposition method, the feature of utilizing ald to grow layer by layer, in the process of growth of zinc oxide thin film, (X can be B, Al, In to mix twice recipient element N and an III main group donor doping element X, Ga), form the zinc-oxide film that acceptor-donor-acceptor is mixed altogether.Donor and acceptor mix the Madelung energy that can reduce system altogether, improve the incorporation of recipient element, and the p-type that is conducive to zinc-oxide film changes.Preparation technology of the present invention is simple, and deposition and doping process are easy to control, and prepare gained and mix altogether the stability that zinc-oxide film is conducive to improve zinc-oxide film p-type electrical properties.
Brief description of the drawings
The ald that Fig. 1 provides for the embodiment of the present invention is prepared III main group donor doping element X and N recipient element and mixes altogether the schema of zinc-oxide film.
Embodiment
Method shown in Figure 1, ald provided by the invention is prepared donor-acceptor and mixed altogether zinc-oxide film, comprising:
Substrate is cooked to substrate pre-treatment, and put into ald chamber chamber;
Chamber is vacuumized, substrate chamber is heated;
In ald chamber chamber, introduce Zn (C
2h
5)
2;
With high pure nitrogen cleaning ald chamber chamber;
In ald chamber chamber, introduce nitrogen gas plasma;
With high pure nitrogen cleaning ald chamber chamber;
In ald chamber chamber, introduce water vapour;
With high pure nitrogen cleaning ald chamber chamber;
In ald chamber chamber, introduce donor doping source of the gas;
With high pure nitrogen cleaning ald chamber chamber;
In ald chamber chamber, introduce Zn (C
2h
5)
2;
With high pure nitrogen cleaning ald chamber chamber;
In ald chamber chamber, introduce nitrogen gas plasma;
With high pure nitrogen cleaning ald chamber chamber;
In ald chamber chamber, introduce water vapour;
With high pure nitrogen cleaning ald chamber chamber.
Below in conjunction with specific embodiment, ald provided by the invention being prepared to donor-acceptor mixes altogether the method for zinc-oxide film and describes.
Embodiment 1:
Silicon substrate or glass substrate are processed with vitriol oil hydrogen peroxide, then cleaned N by ultrapure water ultrasonic wave
2dry up, wherein the vitriol oil: hydrogen peroxide=4:1.Substrate is put into the chamber of ald, opened atomic layer deposition apparatus, adjust working parameter, vacuumize, heat and sink to the bottom, reach the required various Working environments of experiment; Carry out B-N and mix altogether many groups composite deposition of zinc-oxide film, i.e. Zn (C
2h
5)
2/ N
2/ plasma N
2/ N
2/ H
2o/N
2/ BF
3/ N
2/ Zn (C
2h
5)
2/ N
2/ plasmaN
2/ N
2/ H
2o/N
2=0.15s/50s/10s/50s/0.07s/50s/0.08s/50s/0.08s/50s/10s/50s/ 0.07s/50s.Wherein the flow of nitrogen is 1sccm-1000sccm, is preferably 15sccm, and inlet period is 0.04s-5s, is preferably 0.15s, and scavenging period is 5s-150s, is preferably 50s, and underlayer temperature is 100 DEG C-500 DEG C, is preferably 300 DEG C; Wherein plasma discharge power is 1W-100W, is preferably 50W, and be 1s-50s, preferably 10s discharge time.Pass through during this period N
2plasma body is introduced N doping, passes through BF
3provide B atom, twice plasma N
2with a BF
3deposition, make B in ZnO for zinc (B
zn), N substitutes the position of O, forms the complex body of N-Zr-N in film, and this complex body can reduce ionization energy, promotes the formation that p-type electricity is led.Repeat this multi-component composite deposition, the zinc-oxide film that the N-B-N that can successively grow mixes altogether.
Embodiment 2:
Silicon substrate or glass substrate are processed with vitriol oil hydrogen peroxide, then cleaned N by ultrapure water ultrasonic wave
2dry up, wherein the vitriol oil: hydrogen peroxide=4:1.Substrate is put into the chamber of ald, opened atomic layer deposition apparatus, adjust working parameter, vacuumize, heat and sink to the bottom, reach the required various Working environments of experiment; Carry out Al-N and mix altogether many groups composite deposition of zinc-oxide film, i.e. Zn (C
2h
5)
2/ N
2/ plasma N
2/ N
2/ H
2o/N
2/ Al (CH
3)
3/ N
2/ Zn (C
2h
5)
2/ N
2/ plasma N
2/ N
2/ H
2o/N
2=0.15s/50s/10s/50s/0.07s/50s/0.08s/50s/0.08s/50s/10s/50s/ 0.07s/50s.Wherein the flow of nitrogen is 1sccm-1000sccm, is preferably 15sccm, and inlet period is 0.04s-5s, is preferably 0.15s, and scavenging period is 5s-150s, is preferably 50s, and underlayer temperature is 100 DEG C-500 DEG C, is preferably 300 DEG C; Wherein plasma discharge power is 1W-100W, is preferably 50W, and be 1s-50s, preferably 10s discharge time.Pass through during this period N
2plasma body is introduced N doping, by Al (CH
3)
3provide Al atom, twice plasma N
2with an Al (CH
3)
3deposition, make Al in ZnO for zinc (Al
zn), N substitutes the position of O, forms mixing altogether of N-Al-N in zinc-oxide film, repeats this multi-component composite deposition, and the zinc-oxide film that the N-Al-N that can successively grow mixes altogether promotes the formation that p-type electricity is led.
Embodiment 3:
Silicon substrate or glass substrate are processed with vitriol oil hydrogen peroxide, then cleaned N by ultrapure water ultrasonic wave
2dry up, wherein the vitriol oil: hydrogen peroxide=4:1.Substrate is put into the chamber of ald, opened atomic layer deposition apparatus, adjust working parameter, vacuumize, heat and sink to the bottom, reach the required various Working environments of experiment; Carry out In-N and mix altogether many groups composite deposition of zinc-oxide film, i.e. Zn (C
2h
5)
2/ N
2/ plasma N
2/ N
2/ H
2o/N
2/ In (CH
2cH
3)
3/ N
2/ Zn (C
2h
5)
2/ N
2/ plasma N
2/ N
2/ H
2o/N
2=0.15s/50s/10s/50s/0.07s/50s/0.08s/50s/0.08s/50s/10s/50s/ 0.07s/50s.Wherein the flow of nitrogen is 1sccm-1000sccm, is preferably 15sccm, and inlet period is 0.04s-5s, is preferably 0.15s, and scavenging period is 5s-150s, is preferably 50s, and underlayer temperature is 100 DEG C-500 DEG C, is preferably 300 DEG C; Wherein plasma discharge power is 1W-100W, is preferably 50W, and be 1s-50s, preferably 10s discharge time.Pass through during this period N
2plasma body is introduced N doping, by In (CH
2cH
3)
3provide In atom, twice plasma N
2with an In (CH
2cH
3)
3deposition, make In in ZnO for zinc (In
zn), N substitutes the position of O, forms mixing altogether of N-In-N in film, repeats this polycomponent composite deposition, the zinc-oxide film that the N-In-N that can successively grow mixes altogether.Be mixed with to be altogether beneficial to and improve recipient element doping, promote the formation that p-type electricity is led.
Embodiment 4:
Silicon substrate or glass substrate are processed with vitriol oil hydrogen peroxide, then cleaned N by ultrapure water ultrasonic wave
2dry up, wherein the vitriol oil: hydrogen peroxide=4:1.Substrate is put into the chamber of ald, opened atomic layer deposition apparatus, adjust working parameter, vacuumize, heat and sink to the bottom, reach the required various Working environments of experiment; Carry out Ga-N and mix altogether many groups composite deposition of zinc-oxide film, i.e. Zn (C
2h
5)
2/ N
2/ plasma N
2/ N
2/ H
2o/N
2/ Ga (CH
2cH
3)
3/ N
2/ Zn (C
2h
5)
2/ N
2/ plasma N
2/ N
2/ H
2o/N
2=0.15s/50s/10s/50s/0.07s/50s/0.08s/50s/0.08s/50s/10s/50s/ 0.07s/50s.Wherein the flow of nitrogen is 1sccm-1000sccm, is preferably 15sccm, and inlet period is 0.04s-5s, is preferably 0.15s, and scavenging period is 5s-1500s, is preferably 50s, and underlayer temperature is 100 DEG C-500 DEG C, is preferably 300 DEG C; Wherein plasma discharge power is 1W-100W, is preferably 50W, and be 1s-50s, preferably 10s discharge time.Pass through during this period N
2plasma body is introduced N doping, by Ga (CH
2cH
3)
3provide Ga atom, twice plasma N
2with a Ga (CH
2cH
3)
3deposition, make Ga in ZnO for zinc (Ga
zn), N substitutes the position of O, in film, form N-Ga-N mix altogether, repeat this multi-component composite deposition, the zinc-oxide film that the N-Ga-N that can successively grow mixes altogether.Be mixed with to be altogether beneficial to and improve recipient element doping, promote the formation that p-type electricity is led.
The zinc-oxide film that the growth pattern growth III main group element that the present invention successively circulates by ALD and N mix altogether, passes through N during this period
2plasma body generates N atom, provides donor doping atom by III main group element source of the gas, twice plasma N
2with the deposition in a donor doping source, make III main group donor doping element X (X can be B, Al, In, Ga) in ZnO, replace zinc (X
zn), N substitutes the position of O, in film, form N-X-N mix altogether, mix altogether and can reduce ionization energy, be conducive to improve recipient element doping, promote the formation that p-type electricity is led.Repeat this many groups composite deposition, the zinc-oxide film that the N-X-N that can successively grow mixes altogether.
Method provided by the invention can realize III main group donor doping element X, and (X can be B, Al, In, Ga) with the mixing altogether of N element, and method is simple, utilize the feature of ald individual layer cycling deposition, in the process of growth of zinc oxide thin film, realize and in whole membrane structure, adulterating uniformly, zinc-oxide film after donor-acceptor is mixed altogether, can reduction system starve Madelung energy, the doping content that increases N, can also obtain more shallow acceptor level, is conducive to the formation that promotes that p-type electricity is led.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to example, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (10)
1. the method that ald is prepared donor-acceptor and mixed altogether zinc-oxide film, is characterized in that, comprising:
Substrate is put into ALD reaction chamber, substrate and chamber tube are heated, then carry out multi-component composite deposition;
Described composite deposition is included in for the first time after the deposition of zinc source, introduces respectively the doping deposition in the donor doping source that once comprises III main group element X, zinc source deposition, at least twice nitrogen doping source deposition and at least twice oxygen source deposition for the second time, forms mixing altogether of N-X-N; The sedimentary sequence of described nitrogen doping source deposition and described oxygen source is first nitrogen doping source deposition, rear oxygen source deposition; The described III of comprising main group element donor doping source deposition is first to comprise III main group element donor doping source deposition with described zinc for the second time source sedimentary sequence, after zinc source deposition for the second time.
2. preparation method according to claim 1, is characterized in that, described substrate is through the vitriol oil and hydrogen peroxide processing, and through silicon chip, sapphire or the glass of the ultrasonic mistake of ultrapure water, substrate surface is with hydroxyl.
3. preparation method according to claim 2, is characterized in that, described composite deposition comprises:
Under vacuum environment successively with zinc source, nitrogen doping source, oxygen source, the donor doping source that comprises III main group element X for the first time, zinc source, nitrogen doping source and oxygen source deposit and obtain the ZnO film that acceptor-donor-acceptor is mixed altogether for the second time, described zinc for the first time source, nitrogen doping source, oxygen source, the donor doping source that comprises III main group element X and zinc source open-assembly time in sediment chamber is followed successively by 0.15s, 10s, 0.07s, 0.08s, 0.08s for the second time.
4. preparation method according to claim 3, is characterized in that, after each deposition, adopts high pure nitrogen clean deposition chamber, and scavenging period is 50s.
5. according to the preparation method described in claim 1-4 any one, it is characterized in that, described zinc source is to contain the alkylate of zinc or the halogenide containing zinc, and described oxygen source is water vapor or oxygen gas plasma; Described nitrogen doping source is N
2o, N
2, NO, NO
2or NH
3plasma body.
6. preparation method according to claim 5, is characterized in that, the described halogenide containing zinc is zinc chloride ZnCl
2, the described alkylate containing zinc is zinc ethyl Zn (C
2h
5)
2or zinc methide Zn (CH
3)
2.
7. preparation method according to claim 5, it is characterized in that, described in comprise III main group element X donor doping source be containing the halogenide of X, containing the alcoholate of X, containing the alkylide of X, containing the hydride of X, containing the cyclopentadienyl of X, containing the alkane acid amides of X or containing the amidino groups of X.
8. preparation method according to claim 7, is characterized in that, the described halogenide containing X is boron trifluoride BF
3, the described alcoholate containing X is methyl alcohol boron (OCH
3)
3), the described alkylide containing X is trimethyl aluminium Al (CH
3)
3, triethylindium In (CH
2cH
3)
3or triethyl-gallium Ga (CH
2cH
3)
3.
9. preparation method according to claim 5, is characterized in that, also comprises:
Regulate the ratio of nitrogen doping source and oxygen in doping zinc-oxide film by controlling the aeration time of described nitrogen doping source and water vapour.
10. preparation method according to claim 5, is characterized in that, also comprises:
Regulate the ratio of donor doping and zinc in doping zinc-oxide film by controlling the aeration time in III main group element doped source and zinc source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210533506.XA CN103866280B (en) | 2012-12-11 | 2012-12-11 | Method for preparing donor-acceptor co-doped zinc oxide film by atomic layer deposition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210533506.XA CN103866280B (en) | 2012-12-11 | 2012-12-11 | Method for preparing donor-acceptor co-doped zinc oxide film by atomic layer deposition |
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| Publication Number | Publication Date |
|---|---|
| CN103866280A true CN103866280A (en) | 2014-06-18 |
| CN103866280B CN103866280B (en) | 2016-10-05 |
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| KR20090108552A (en) * | 2008-04-11 | 2009-10-15 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Preparation of metal oxide thin film via cyclic cvd or ald |
| CN102017104A (en) * | 2007-09-26 | 2011-04-13 | 伊斯曼柯达公司 | Process for making doped zinc oxide |
| CN102304700A (en) * | 2011-09-23 | 2012-01-04 | 中国科学院微电子研究所 | Preparation method of nitrogen-doped zinc oxide film |
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| CN102017104A (en) * | 2007-09-26 | 2011-04-13 | 伊斯曼柯达公司 | Process for making doped zinc oxide |
| KR20090108552A (en) * | 2008-04-11 | 2009-10-15 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Preparation of metal oxide thin film via cyclic cvd or ald |
| CN102304700A (en) * | 2011-09-23 | 2012-01-04 | 中国科学院微电子研究所 | Preparation method of nitrogen-doped zinc oxide film |
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| WO2024067635A1 (en) * | 2022-09-30 | 2024-04-04 | 华为技术有限公司 | Composite thin film, and preparation method therefor and use thereof |
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