CN105525268A - Method for improving mobility ratio and stability of ZnON thin film - Google Patents
Method for improving mobility ratio and stability of ZnON thin film Download PDFInfo
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- CN105525268A CN105525268A CN201610059148.1A CN201610059148A CN105525268A CN 105525268 A CN105525268 A CN 105525268A CN 201610059148 A CN201610059148 A CN 201610059148A CN 105525268 A CN105525268 A CN 105525268A
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000010409 thin film Substances 0.000 title abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 81
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000001301 oxygen Substances 0.000 claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052786 argon Inorganic materials 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 239000011229 interlayer Substances 0.000 claims abstract description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 9
- 239000013077 target material Substances 0.000 claims abstract description 6
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 4
- 238000005477 sputtering target Methods 0.000 claims abstract description 4
- 238000000137 annealing Methods 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 26
- 238000004544 sputter deposition Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 9
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- -1 vacuum Substances 0.000 claims description 3
- 238000007039 two-step reaction Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 8
- 239000010410 layer Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 70
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001341 grazing-angle X-ray diffraction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0084—Producing gradient compositions
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses a method for improving the mobility ratio and the stability of a ZnON thin film. The method comprises the following steps that the ZnON thin film of a sandwich structure is adopted, the interlayer on a substrate of the sandwich structure is a nitrogen-rich ZnON thin film, and the covering layer on the interlayer is an oxygen-rich ZnON thin film; the ZnON thin film of the sandwich structure is prepared through reactive radio frequency magnetron sputtering, and a zinc target with purity being 99.999% is used as a sputtering target material; before the ZnON thin film is grown, the high-purity zinc target material is pre-sputtered for 5-15 minutes through argon ion beams; through the two-step reactive radio frequency magnetron sputtering growing method, specifically, firstly, a prepared amorphous nitrogen-rich ZnON thin film is grown, and secondly, an oxygen-rich ZnON polycrystalline thin film is prepared, so that the defect density of the inner side of a thin film body and the defect density of a grain boundary are reduced; accordingly, the ZnON thin film material with high mobility ratio and high stability is obtained.
Description
Technical field
The present invention relates to technical field of semiconductors, particularly relate to a kind of method improving ZnON film mobility and stability.
Background technology
Along with the development of information display technology, liquid-crystal display has been dispersed throughout in daily life and work.Flat-panel display device high to miniaturization, lightweight, quality, consume energy the future development such as low, and thin film transistor is the core driving element of technique of display, therefore, prepare high mobility, high stability the development of thin film transistor channel material to novel information technique of display most important.
The driving element of liquid-crystal display is mainly with amorphous silicon film transistor, low-temperature polysilicon film transistor and the amorphous oxide thin film transistor that is representative with indium gallium zinc oxygen in the market.Amorphous silicon film transistor has the advantages such as homogeneity, production cost be low, but the low (~ 1cm of the mobility of non-crystalline silicon
2/ Vs), the shortcoming such as poor stability; Low-temperature polysilicon film transistor has mobility advantages of higher, but the lack of homogeneity of low temperature polycrystalline silicon, and be unfavorable for big area manufacture, production cost is high.Therefore, silicon-based film transistor can not meet with the requirement of high resolving power, large size and the high frame number information displaying of future generation that is feature.Although indium gallium zinc oxygen thin film transistor well solves the problem of non-crystalline silicon mobility and low temperature polycrystalline silicon lack of homogeneity, but because the defect concentration such as Lacking oxygen of indium gallium zinc oxygen is higher, there is Persistent Photocurrent, manufacturing process reproducibility is poor, the repeatability of thin film transistor and the stability under illumination, bias voltage, atmosphere need to improve, and indium gallium zinc oxygen thin film transistor contains the thulium such as indium, gallium, this is by the reduction of serious limit production cost.Therefore people actively find the material that a new generation has premium properties, high mobility, as the channel material of thin film transistor.
The currently reported development about ZnON base high mobility thin film transistor, and the backboard being used successfully to 3.8 inches of QVGA displays drives.Compared with indium gallium zinc oxygen, ZnON has following advantage: (1) electron effective mass is little, and mobility is high; (2) shielding Lacking oxygen by raising valence band, defect concentration in band being reduced, it also avoid the generation of Persistent Photocurrent simultaneously; (3) stability under light illumination significantly improves; (4) be easy to big area manufacture, abundant raw materials, preparation method is simple and reliable.ZnON still belongs to novel amorphous oxide material, is still in the junior stage to the research of its physical characteristics of materials, and especially the chemical stability of ZnON material and structural stability are effectively solved not yet.So to the further research of ZnON material, the mobility and the stability that improve ZnON are most important, and this will dominate the development of technique of display of future generation.
Summary of the invention
The object of the invention is to propose and a kind ofly improve the mobility of ZnON film and the method for stability, solve the problem of ZnON film ageing failure in atmosphere, improve mobility and the stability of ZnON film simultaneously, laying a solid foundation for preparing thin film transistor of good performance, being expected to realize the future development of technique of display of future generation to high resolving power, large size, high frame number.
The present invention solves problem by the following technical programs: a kind of method improving ZnON film mobility and stability, it is characterized in that, comprise the following steps: the ZnON film adopting sandwich structure, the suprabasil interlayer of sandwich structure is rich nitrogen ZnON film 2, the tectum on interlayer top is oxygen enrichment ZnON film 3, reactive radio frequency magnetron sputtering is adopted to prepare the ZnON film (heterojunction) of sandwich structure, be that the zinc target of 99.999% is for sputtering target material with purity, with argon gas, nitrogen, the mixed gas of oxygen is sputter gas, before growth ZnON film, the background vacuum pressure of sputtering chamber is less than 2 × 10
-7torr, with the air in emptying sputtering chamber, radio frequency power is 120-300W, and underlayer temperature is room temperature to 100 DEG C, utilizes ar-ion beam pre-sputtering 5-15 minute before growth ZnON film to high purity zinc target, by the method that two-step reaction rf magnetron sputtering grows, the first step: the flow of argon gas, nitrogen, oxygen is respectively 20sccm, 100sccm, 0.8-5sccm, film thickness is 20-150 nanometer, and the first step growth obtains the ZnON film 2 of the rich nitrogen of one deck, second step: the flow of argon gas, nitrogen, oxygen is respectively 20sccm, 100sccm, 8-20sccm, second step growth obtains the ZnON film 3 of one deck oxygen enrichment, and film thickness is 5-30 nanometer.
The purity of described sputter gas is 99.999%.
In the process of sputtering, sputtering chamber pressure remains 4-20mTorr.
Before described growth ZnON film, the power of pre-sputtering is 120-300W.
In sandwich structure, the nitrogen of the rich nitrogen ZnON and tectum oxygen enrichment ZnON of interlayer and argon flow amount are fixed as 100sccm and 20sccm, and oxygen flow is respectively 0.8-5sccm and 8-20sccm.
Under different atmosphere, differing temps, carry out anneal to the ZnON film of growth, described different atmosphere is nitrogen, vacuum, nitrous oxide and oxygen; Described differing temps is 250 DEG C-500 DEG C.
Annealing time is 60 minutes, and temperature rise rate is 30 DEG C/min, naturally cools to room temperature.
Compare the result reported now, beneficial effect of the present invention:
(1) two-step growth method is adopted: in the first step sandwich structure, the rich nitrogen ZnON of interlayer and second step original position prepare tectum oxygen enrichment ZnON, improve the stability of transistor channel layer, suppress the function degradation of subsequent crystallographic tube device.Have studied after not having the ZnON film of tectum oxygen enrichment ZnON to place 90 days in atmosphere and become ZnO completely.
(2) to the annealing 60 minutes in nitrogen or vacuum, within the scope of 300 DEG C ~ 350 DEG C of the ZnON film of growth, mobility can be obtained up to 77.6cm
2/ vs.
(3) all non-considerable change after 200 days placed in atmosphere by described ZnON film sample that is no matter unannealed or annealing, and the stability of ZnON film obtains obvious lifting.
Accompanying drawing explanation
Fig. 1 is the ZnON film of sandwich structure prepared by employing two-step growth method of the present invention.
Fig. 2 is the Hall test result of ZnON film of the present invention, in figure (a): ZnON film 300 DEG C, anneal under different annealing atmosphere 1h; (b): ZnON film is annealed under differing temps 1h in a vacuum.
Fig. 3 is the GIXRD figure of 500 DEG C of annealing 1h in 300 DEG C of anneal 1h and vacuum in the unannealed sample of ZnON film of the present invention, vacuum.
Fig. 4 is the Raman scattering spectra of 500 DEG C of annealing 1h in 300 DEG C of anneal 1h and vacuum in the unannealed sample of ZnON film of the present invention, vacuum.
Fig. 5 is the SEM figure of ZnON film of the present invention, in figure (a): unannealed sample; (b): 300 DEG C of annealing 1h in vacuum; (c): 500 DEG C of annealing 1h in vacuum.
Embodiment
The present invention proposes and a kind ofly improve the mobility of ZnON film and the method for stability, below in conjunction with specific embodiments and the drawings, it is further described.
Improve the method for ZnON film mobility and stability, comprise following general step:
Select silicon chip, quartz, glass or flexible substrate as the substrate of growth ZnON film; Adopt reactive radio frequency magnetron sputtering, with purity be the zinc target of 99.999% for sputtering target material, with the mixed gas of argon gas, nitrogen, oxygen for sputter gas, the background vacuum pressure of sputtering chamber is less than 2 × 10
-7torr, with the air in emptying sputtering chamber, radio frequency power is 120-300W, underlayer temperature is room temperature to 100 DEG C, before growth ZnON film, ar-ion beam pre-sputtering is utilized 15 minutes to high purity zinc target, the pollutent of effective removal target material surface, reduces the impurity concentration in growing film and the crystal mass improving film.The present invention adopts two-step growth method to prepare oxygen enrichment ZnON/ rich nitrogen ZnON sandwich structure.The first step grows: the flow of argon gas, nitrogen, oxygen is respectively 20sccm, 100sccm, 0.8-5sccm, and film thickness is 20-150 nanometer; Second step grows: the flow of argon gas, nitrogen, oxygen is respectively 20sccm, 100sccm, 8-20sccm, and film thickness is 5-30 nanometer.Finally under different atmosphere, differing temps, anneal is carried out to the ZnON film of growth, thus obtain the ZnON thin-film material with high mobility, high stability.
Comparatively preferred, first pre-sputtering before growth ZnON film, pre-sputtering selects argon gas to be working gas, is advisable with 15 minutes, to remove the pollutent on zinc target surface, reduces impurity concentration in ZnON film further, improves the quality of ZnON film.
Comparatively preferred, the present invention adopts two-step growth method, the first step growth obtains the ZnON film 2 of the rich nitrogen of one deck, second step growth obtains the ZnON film 3 of one deck oxygen enrichment, and the ZnON film of oxygen enrichment has insulation, fine and close feature, difficulty reacts with the oxygen in air and moisture, thus improves the stability of ZnON film.
Comparatively preferred, the flow of the first step growth oxygen is 0.8-1.5sccm, and the flow of second step growth oxygen is 8-12sccm.
Further, carry out anneal to the ZnON film of growth, annealing atmosphere is respectively nitrogen, vacuum, nitrous oxide and oxygen; Annealing temperature is respectively 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C and 500 DEG C; The time of annealing is 30 minutes and 60 minutes.
Comparatively preferred, described annealing atmosphere is advisable with reducing atmosphere nitrogen and vacuum, and annealing temperature is 300 DEG C ~ 350 DEG C, and annealing time is 60 minutes.
The process of growth of ZnON film and the concrete operation step of after annealing treating processes as follows:
Step 1: select silicon chip as the substrate of growth ZnON film, silicon face has the silicon-dioxide of one deck thermooxidizing 200nm;
Step 2: select magnetron sputtering equipment, zinc target is as zinc source, and oxygen is as oxygen source, and nitrogen is as nitrogenous source, and argon gas is as shielding gas, and be placed on by cleaned substrate on the substrate pallet of magnetron sputtering equipment, concrete cleaning process is as follows:
(1) substrate is placed in beaker 1, adds appropriate deionized water, ultrasonic cleaning 10min;
(2) substrate is placed in beaker 2, adds appropriate acetone soln, ultrasonic cleaning 10min;
(3) substrate is placed in beaker 3, adds appropriate spirituous solution, ultrasonic cleaning 10min;
(4) substrate is placed in beaker 1, adds appropriate deionized water, ultrasonic cleaning 10min;
(5) dry up with high pure nitrogen.
Wherein, beaker 1 is the beaker of special washed with de-ionized water sample, and beaker 2 is specially with the beaker of acetone soln cleaning sample, and beaker 3 is specially with the beaker of spirituous solution cleaning sample.
Step 3: the vacuum of sputtering chamber is evacuated to 2 × 10
-7below Torr, with the air in emptying sputtering chamber.
Step 4: underlayer temperature is adjusted to room temperature-100 DEG C, radio frequency power is adjusted to 120-300W, is filled with the argon gas that flow is 5-20sccm, pre-sputtering process 15 minutes, to remove the pollutent on zinc target surface.
Step 5: the mixed gas being filled with argon gas, nitrogen and oxygen, its flow is respectively 20sccm, 100sccm and 1.5sccm, and pressure is 4mTorr, and start the first step growth, growth time is 10min.
Step 6: the mixed gas being filled with argon gas, nitrogen and oxygen, its flow is respectively 20sccm, 100sccm and 8sccm, and pressure is 4mTorr, and start second step growth, growth time is 5min.
Step 7: growth terminates, and is down to room temperature, takes out sample.
Step 8: cleaned ZnON film is placed in quartz boat, quartz boat is put into reaction chamber, the process of concrete cleaning sample is as follows:
(1) substrate is placed in beaker 2, adds appropriate acetone soln, ultrasonic cleaning 10min;
(2) substrate is placed in beaker 3, adds appropriate spirituous solution, ultrasonic cleaning 10min;
(3) dry up with high pure nitrogen.
Step 9: vacuumize and to make in reaction chamber pressure drop to below 0.45Torr, pass into purity be 99.999% high pure nitrogen make pressure return to normal pressure, vacuumize again and to make in reaction chamber pressure drop to below 0.45Torr, vacuumize again by passing into high pure nitrogen under vacuum conditions, with the air of the remnants in emptying reaction chamber.
Step 10: open heating power supply switch, arranging temperature rise rate is 30 DEG C/min, and annealing temperature is 300 DEG C, and annealing time is 1h, starts to anneal in a vacuum.
Step 11: after annealing terminates, closes heating power supply switch, naturally cools to after room temperature, pass into high pure nitrogen (purity is 99.999%), make the pressure in reaction chamber return to normal pressure, open cavity in reaction chamber until sample, takes out sample.
Fig. 1: adopt two-step growth method to prepare the ZnON film of sandwich structure, in sandwich structure, interlayer is rich nitrogen ZnON film 2 and tectum is oxygen enrichment ZnON film 3, significantly improves the stability into annealing specimen.
Fig. 2: utilize Hall test, study annealing atmosphere of the present invention and annealing temperature to the impact of ZnON Electrical character, as shown in Fig. 1 (a), the mobility of ZnON film, carrier concentration and specific conductivity are 300 DEG C, the annealing test result of 60 minutes in different atmosphere, as can be seen from the figure, best annealing atmosphere is nitrogen or vacuum; As shown in Fig. 1 (b), the mobility of ZnON film, carrier concentration and specific conductivity in a vacuum, annealing after 60 minutes under different annealing temperature, place the test result of 0 day and 200 days in atmosphere, as can be seen from the figure, the ZnON heterojunction that the present invention adopts two-step growth method to prepare sandwich structure significantly improves the stability of unannealed sample, and its mobility tested by unannealed sample after placing 200 days be in atmosphere 41.3cm
2/ Vs, and the ZnON of harsh length (its mobility is 44.1cm
2/ Vs) to compare mobility almost constant.Best annealing temperature window is 300 DEG C-350 DEG C.ZnON film in a vacuum, 300 DEG C annealing 60 minutes, mobility is up to 77.6cm
2/ Vs, and the sample of annealing places 200 days rear stabilities very well in atmosphere, and mobility chance is constant.We analyze its mechanism and are: when annealing temperature is less than 350 DEG C, ion or defect local are at grain boundaries, crystal boundary serves as the formation that trap trapped electron result in potential barrier, along with annealing temperature raise, grain boundaries defect concentration reduce, boundary barrier potential reduce, thus result in the rising of mobility, temperature continues to raise, and crystal boundary is oxidized, and the energy gap of ZnO is greater than Zn
3n
2energy gap, boundary barrier potential increase, mobility reduce.
Fig. 3: utilize grazing incidence X-ray diffraction (GIXRD) to study the crystalline structure of 500 DEG C of annealing 1h in 300 DEG C of anneal 1h and vacuum in the unannealed sample of ZnON film of the present invention, vacuum, as can be seen from the figure, along with annealing temperature raises, the peak of ZnO strengthens gradually, Zn
3n
2peak relatively weaken, the Hall test result before this is positive corresponding.
Fig. 4: utilize Raman (Raman) scattering spectra to study the crystal mass of 500 DEG C of annealing 1h in 300 DEG C of anneal 1h and vacuum in the unannealed sample of ZnON film of the present invention, vacuum further, as can be seen from the figure, the sample of 500 DEG C of annealing obviously can see Si302cm
-1substrate peak and ZnO437cm
-1the peak of E2 (high), this all indicates the ZnON film diffusion of the oxygen in the ZnON film of oxygen enrichment under 500 DEG C of annealing conditions to rich nitrogen, thus the ZnON film that result in rich nitrogen is oxidized.During owing to being greater than 350 DEG C when annealing temperature, Zn-N key starts fracture, and N starts to escape to overflow, and simultaneous point defect and grain boundary defects increase in the process, 274cm
-1for gap zinc cluster, 580cm
-1for the peak relevant with Lacking oxygen, at Zn-N bond rupture and oxygen from the ZnON film of oxygen enrichment to the process of the ZnON film diffusion of rich nitrogen, gap zinc cluster and Lacking oxygen are on the increase, thus result in 274cm
-1, 580cm
-1peak strengthens.
Fig. 5: for further understanding the impact of annealing on ZnON film, Fig. 5 utilizes scanning electronic microscope (SEM) figure to study the unannealed sample of ZnON film of the present invention, in vacuum 300 DEG C annealing 1h and vacuum in 500 DEG C annealing 1h surface topography, as can be seen from the figure, to compare unannealed sample surface morphology almost constant for the sample of 300 DEG C of annealing, and there is a lot of pitting in the sample surfaces of 500 DEG C of annealing, owing to raising along with annealing temperature, the surface energy of sample reduces, the constraint effect of sample surfaces to nitrogen obviously weakens, nitrogen is constantly escaped to overflow, therefore, a lot of pitting is left at sample surfaces.As can be seen from SEM figure equally, along with annealing temperature raises, ZnON film is oxidized gradually.
Above content is in conjunction with concrete embodiment further description made for the present invention.The present invention is not limited to above-mentioned embodiment, if do not depart from the spirit and scope of the present invention to various change of the present invention or distortion, if these are changed and distortion belongs within claim of the present invention and equivalent technologies scope, then the present invention is also intended to comprise these changes and distortion.
Claims (7)
1. one kind is improved the method for ZnON film mobility and stability, it is characterized in that, comprise the following steps: the ZnON film adopting sandwich structure, the suprabasil interlayer of sandwich structure is rich nitrogen ZnON film, the tectum on interlayer top is oxygen enrichment ZnON film, reactive radio frequency magnetron sputtering is adopted to prepare the ZnON film (heterojunction) of sandwich structure, be that the zinc target of 99.999% is for sputtering target material with purity, with the mixed gas of argon gas, nitrogen, oxygen for sputter gas, before growth ZnON film, the background vacuum pressure of sputtering chamber is less than 2 × 10
-7torr, with the air in emptying sputtering chamber, radio frequency power is 120-300W, and underlayer temperature is room temperature to 100 DEG C, utilizes ar-ion beam pre-sputtering 5-15 minute before growth ZnON film to high purity zinc target; By the method that two-step reaction rf magnetron sputtering grows, the first step: the flow of argon gas, nitrogen, oxygen is respectively 20sccm, 100sccm, 0.8-5sccm, film thickness is 20-150 nanometer, and the first step growth obtains the ZnON film of the rich nitrogen of one deck; Second step: the flow of argon gas, nitrogen, oxygen is respectively 20sccm, 100sccm, 8-20sccm, second step growth obtains the ZnON film of one deck oxygen enrichment, and film thickness is 5-30 nanometer.
2. the method for raising ZnON film mobility according to claim 1 and stability, is characterized in that: the purity of described sputter gas is 99.999%.
3. the method for raising ZnON film mobility according to claim 2 and stability, it is characterized in that: in the process of sputtering, sputtering chamber pressure remains 4-20mTorr.
4. the method for raising ZnON film mobility according to claim 2 and stability, is characterized in that: before described growth ZnON film, the power of pre-sputtering is 120-300W.
5. the method for raising ZnON film mobility according to claim 1 and stability, it is characterized in that: in sandwich structure, the nitrogen of the rich nitrogen ZnON and tectum oxygen enrichment ZnON of interlayer and argon flow amount are fixed as 100sccm and 20sccm, and oxygen flow is respectively 0.8-5sccm and 8-20sccm.
6. the method for raising ZnON film mobility according to claim 1 and stability, it is characterized in that: under different atmosphere, differing temps, carry out anneal to the ZnON film of growth, described different atmosphere is nitrogen, vacuum, nitrous oxide and oxygen; Described differing temps is 250 DEG C-500 DEG C.
7. the method for raising ZnON film mobility according to claim 1 and stability, it is characterized in that: annealing time is 60 minutes, temperature rise rate is 30 DEG C/min, naturally cools to room temperature.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106384768A (en) * | 2016-11-18 | 2017-02-08 | Tcl集团股份有限公司 | ZnON, QLED device and manufacturing method thereof |
| CN111554810A (en) * | 2020-05-15 | 2020-08-18 | 中国人民解放军国防科技大学 | Gating device and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461044A (en) * | 2003-06-11 | 2003-12-10 | 浙江大学 | Method for preparing p-type zinc oxide film |
| JP2006144053A (en) * | 2004-11-17 | 2006-06-08 | Bridgestone Corp | METHOD FOR FORMING N-DOPED ZnO FILM |
| CN101599363A (en) * | 2009-04-09 | 2009-12-09 | 上海工程技术大学 | A kind of preparation method of nitrogen-doped zinc oxide p-type diluted magnetic semiconductor material |
| CN103147039A (en) * | 2007-04-27 | 2013-06-12 | 应用材料公司 | Thin film semiconductor material produced through reactive sputtering of zinc target using nitrogen gases |
| CN103474356A (en) * | 2013-09-17 | 2013-12-25 | 深圳丹邦投资集团有限公司 | Method for preparing nitrogen oxygen zinc thin film |
-
2016
- 2016-01-28 CN CN201610059148.1A patent/CN105525268A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461044A (en) * | 2003-06-11 | 2003-12-10 | 浙江大学 | Method for preparing p-type zinc oxide film |
| JP2006144053A (en) * | 2004-11-17 | 2006-06-08 | Bridgestone Corp | METHOD FOR FORMING N-DOPED ZnO FILM |
| CN103147039A (en) * | 2007-04-27 | 2013-06-12 | 应用材料公司 | Thin film semiconductor material produced through reactive sputtering of zinc target using nitrogen gases |
| CN101599363A (en) * | 2009-04-09 | 2009-12-09 | 上海工程技术大学 | A kind of preparation method of nitrogen-doped zinc oxide p-type diluted magnetic semiconductor material |
| CN103474356A (en) * | 2013-09-17 | 2013-12-25 | 深圳丹邦投资集团有限公司 | Method for preparing nitrogen oxygen zinc thin film |
Non-Patent Citations (1)
| Title |
|---|
| FUMIYA WATANABE,ET AL.: ""Rapid thermal annealing of sputter-deposited ZnO/ZnO:N/ZnO multilayered structures"", 《THIN SOLID FILMS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106384768A (en) * | 2016-11-18 | 2017-02-08 | Tcl集团股份有限公司 | ZnON, QLED device and manufacturing method thereof |
| CN106384768B (en) * | 2016-11-18 | 2019-04-16 | Tcl集团股份有限公司 | A kind of ZnON, QLED device and preparation method thereof |
| CN111554810A (en) * | 2020-05-15 | 2020-08-18 | 中国人民解放军国防科技大学 | Gating device and preparation method thereof |
| CN111554810B (en) * | 2020-05-15 | 2023-04-07 | 中国人民解放军国防科技大学 | Gating device and preparation method thereof |
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