CN103866267B - The preparation method of zinc-oxide film it is co-doped with for N-Zr - Google Patents
The preparation method of zinc-oxide film it is co-doped with for N-Zr Download PDFInfo
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- CN103866267B CN103866267B CN201210531516.XA CN201210531516A CN103866267B CN 103866267 B CN103866267 B CN 103866267B CN 201210531516 A CN201210531516 A CN 201210531516A CN 103866267 B CN103866267 B CN 103866267B
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Abstract
The present invention discloses a kind of preparation method being co-doped with zinc-oxide film for N Zr, including being put into by substrate in ALD reaction chamber, heats substrate and chamber tube, then carries out multi-component composite deposition；After described composite deposition is included in first time zinc source deposition, introduce the doping deposition of the doped source once containing doped chemical Zr, for the second time zinc source deposition respectively, twice nitrogen doping source deposits and twice oxygen source deposition, and formation N Zr N is co-doped with；The sedimentary sequence of described nitrogen doping source deposition and described oxygen source is first nitrogen doping source deposition, and rear oxygen source deposits；The described doped source deposition containing doped chemical Zr and described second time zinc source sedimentary sequence are the doped source depositions first containing doped chemical Zr, rear second time zinc source deposition.The method can carry out being co-doped with of alms giver acceptor in situ to zinc-oxide film, to increase the incorporation of recipient element, promotes that the p-type of zinc-oxide film changes.
Description
Technical field
The present invention relates to the preparing technical field of zinc-oxide film, be co-doped with oxidation particularly to for N-Zr
The preparation method of zinc film.
Background technology
Semiconductive thin film has been given play to the heaviest in the new high-tech industries such as microelectronics, optics, informatics
The effect wanted, the development preparation of high-crystal quality semiconductive thin film and doping techniques, especially for the
The preparation of three generations's semi-conducting material ZnO film, characterize, adulterate extremely characteristic research, for including purple
Outer wave band luminescent material, ultraviolet detector, high integration photonic propulsion and electronics device, solar-electricity
Ponds etc. are of great significance towards the important applied field tool of new forms of energy.Zinc oxide is new as one
II-VI race's direct band gap high-gap compound of type, has big room temperature energy gap 3.37eV,
And free exciton combines and can be up to 60meV, is increasingly subject to people's attention as semi-conducting material.
Compared with other semiconductor material with wide forbidden band, ZnO film growth temperature is low, and radiation resistance is good, is excited
Radiation has relatively low threshold power and the highest energy conversion efficiency, and these advantages make ZnO just become light
The new and high technologies such as electronics, microelectronics, information are rely after 12 and are continued the key foundation material of development
Material.But intrinsic ZnO is due to existing defects so that ZnO is N-shaped, the preparation of p-type ZnO film is
The focus of ZnO correlative study at present and difficult point.Although the calculating that N doping is in theory makes p-type ZnO
Preparation be possibly realized, but numerous experiment shows, owing to N element solid solubility in ZnO is relatively low,
Therefore individually N element doping can not realize the p-type ZnO film of high carrier concentration and high mobility.
In order to solve this problem, it is co-doped with being considered as to prepare high-quality p-ZnO film optimum development prospect
One of direction.
In recent years, the method preparing ZnO film generally includes: such as magnetron sputtering, Organometallic Chemistry
Vapour deposition (MOCVD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD) and wet-chemical deposition etc..
These preparation technologies are respectively arranged with pluses and minuses, the film prepared with MOCVD and MBE method from the point of view of crystallization situation
Quality is preferable.But, MOCVD can not carry out the doping of film and rapid present in reacting in position
Stream and air flow method can affect thickness and the uniformity of film.MBE technology is for specific atoms layer position
Accurately doping is also difficult to.
Summary of the invention
The technical problem to be solved is to provide a kind of can carrying out zinc-oxide film in situ
Be co-doped with, to increase the incorporation of recipient element, promote zinc-oxide film p-type change for N-Zr
It is co-doped with the preparation method of zinc-oxide film.
For solving above-mentioned technical problem, the invention provides and a kind of be co-doped with zinc-oxide film for N-Zr
Preparation method, including being put into by substrate in ALD reaction chamber, heats substrate and chamber tube,
Then multi-component composite deposition is carried out；After described composite deposition is included in first time zinc source deposition, point
Do not introduce the doping deposition of the doped source once containing doped chemical Zr, for the second time zinc source deposition, twice nitrogen
Doped source deposition and twice oxygen source deposition, form being co-doped with of N-Zr-N；Described nitrogen doping source deposition and institute
The sedimentary sequence stating oxygen source is first nitrogen doping source deposition, and rear oxygen source deposits；Described Zr deposition and described the
Secondary zinc source sedimentary sequence is the doped source deposition first containing doped chemical Zr, rear second time zinc source deposition.
The preparation method being co-doped with zinc-oxide film for N-Zr that the present invention provides, utilizes ald
The feature grown layer by layer, during growth of zinc oxide thin film, mixes twice recipient element N and
Secondary Zr, forms the zinc-oxide film that N-Zr-N is co-doped with.The formation of N-Zr-N complex, reduce from
Change energy, promote the formation of p-type conductance.Preparation technology of the present invention is simple, deposits and doping process is prone to
Control, prepare gained and be co-doped with the steady of zinc-oxide film beneficially raising zinc-oxide film p-type electrical properties
Qualitative.
Accompanying drawing explanation
The stream of the preparation method being co-doped with zinc-oxide film for N-Zr that Fig. 1 provides for the embodiment of the present invention
Cheng Tu.
Detailed description of the invention
The preparation side being co-doped with zinc-oxide film for N-Zr shown in Figure 1, that the embodiment of the present invention provides
Method, including: silicon substrate or glass substrate concentrated sulfuric acid hydrogen peroxide are processed, then uses ultra-pure water
Ultrasonic wave is carried out, N2Dry up, wherein the concentrated sulfuric acid: hydrogen peroxide=4:1.Place the substrate into atomic layer
In the chamber of deposition, open atomic layer deposition apparatus, adjust running parameter, vacuumize, heat and sink to the bottom,
Reach the required various working environments of experiment；Carry out N-Zr and be co-doped with many groups composite deposition of zinc-oxide film,
I.e. Zn (C2H5)2/N2/plasma N2/N2/H2O/N2/(CH3CH2O)4Zr/N2/Zn(C2H5)2
/N2/plasma N2/N2/H2O/N2=0.15s/50s/10s/50s/0.07s/50s/0.08
s/50s/0.08s/50s/10s/50s/0.07s/50s.Wherein the flow of nitrogen is 1
Sccm-1000sccm, it is therefore preferable to 15sccm, inlet period is 0.04s-5s, it is therefore preferable to 0.15
S, scavenging period is 5s-150s, it is therefore preferable to 50s, and underlayer temperature is 100 DEG C-500 DEG C, excellent
Selection of land is 300 DEG C；Wherein plasma discharge power is 1W-100W, it is therefore preferable to 50W, electric discharge
Time is 1s-50s, preferably 10s.Pass through N during this period2Plasma introduces N doping,
By (CH3CH2O)4Zr provides Zr atom, twice plasma N2Once (CH3CH2O)4Zr's is heavy
Long-pending so that Zr replaces zinc (Zr in ZnOZn), N substitutes the position of O, forms N-Zr-N's in the film
Complex, this complex can reduce ionization energy, promotes the formation of p-type conductance.Repeat this multi-component
Composite deposition, can successively grow the zinc-oxide film that N-Zr-N is co-doped with.
The zinc-oxide film that growth pattern growth Zr with N that the present invention is successively circulated by ALD is co-doped with,
And method is simple, utilizes the feature of ald individual layer cycling deposition, at growth of zinc oxide thin film
During realize being doped in whole membrane structure uniformly, the zinc-oxide film after being co-doped with,
May advantageously facilitate the formation of p-type conductance.
It should be noted last that, above detailed description of the invention is only in order to illustrate technical scheme
And unrestricted, although the present invention being described in detail with reference to example, the ordinary skill people of this area
Member should be appreciated that and can modify technical scheme or equivalent, without deviating from
The spirit and scope of technical solution of the present invention, it all should be contained in the middle of scope of the presently claimed invention.
Claims (6)
1. the preparation method being co-doped with zinc-oxide film for N-Zr, it is characterised in that including:
Substrate is put in ALD reaction chamber, substrate and chamber tube are heated, then carry out
Multi-component composite deposition；
Described composite deposition deposits with zinc source deposition for the first time, nitrogen doping source deposition, oxygen source, contains successively
The doping deposition of the doped source of doped chemical Zr, for the second time zinc source deposition, nitrogen doping source deposition and oxygen
Source deposition forms being co-doped with of N-Zr-N；Described nitrogen doping source deposition and the sedimentary sequence of described oxygen source
Being first nitrogen doping source deposition, rear oxygen source deposits；The described doped source containing doped chemical Zr deposits and institute
Stating second time zinc source sedimentary sequence is the doped source deposition first containing doped chemical Zr, rear second time zinc source
Deposition；
Wherein, described zinc source is Zn (C2H5)2, described nitrogen doping source is N2Plasma, described Zr
Doped source be (CH3CH2O)4Zr, described oxygen source is steam.
Preparation method the most according to claim 1, it is characterised in that described substrate is through dense
Sulfuric acid and hydrogen peroxide process, and through silicon chip, sapphire or the glass of the ultrasonic mistake of ultra-pure water, substrate surface
With hydroxyl.
Preparation method the most according to claim 2, it is characterised in that described composite deposition bag
Include:
The most successively with for the first time zinc source, nitrogen doping source, oxygen source, containing doped chemical Zr
Doped source, for the second time zinc source, nitrogen doping source and oxygen source carry out depositing that to obtain the ZnO that N-Zr is co-doped with thin
Film, described first time zinc source, nitrogen doping source, oxygen source, containing doped chemical Zr doped source and second time zinc
Source open-assembly time in settling chamber is followed successively by 0.15s, 10s, 0.07s, 0.08s, 0.08s.
Preparation method the most according to claim 3, it is characterised in that after deposition every time
Using high pure nitrogen to clean settling chamber, scavenging period is 50s.
Preparation method the most according to claim 1, it is characterised in that also include:
Doping zinc-oxide film is regulated by the duration of ventilation of the nitrogen doping source described in control with steam
Middle nitrogen doping source and the ratio of oxygen.
Preparation method the most according to claim 1, it is characterised in that also include:
Doping oxidation is regulated by the duration of ventilation of the control doped source containing doped chemical Zr with zinc source
Zirconium doped source and the ratio of zinc in zinc film.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102534501A (en) * | 2012-03-29 | 2012-07-04 | 山东理工大学 | Preparation method for co-doped zinc oxide transparent conductive thin film for solar cell |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7875559B2 (en) * | 2007-01-09 | 2011-01-25 | Electronics And Telecommunications Research Institute | Method of manufacturing P-type ZnO semiconductor layer using atomic layer deposition and thin film transistor including the P-type ZnO semiconductor layer |
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- 2012-12-11 CN CN201210531516.XA patent/CN103866267B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102534501A (en) * | 2012-03-29 | 2012-07-04 | 山东理工大学 | Preparation method for co-doped zinc oxide transparent conductive thin film for solar cell |
Non-Patent Citations (1)
| Title |
|---|
| "Pulsed laser deposition of Zr–N codoped p-type ZnO thin films";H. Kim et al.;《Applied Physics A》;20080613;第93卷;第593-598页 * |
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