CN104195552A - Method for manufacturing vanadium dioxide thin film having high resistance change rate on silicon base - Google Patents

Method for manufacturing vanadium dioxide thin film having high resistance change rate on silicon base Download PDF

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CN104195552A
CN104195552A CN201410338437.6A CN201410338437A CN104195552A CN 104195552 A CN104195552 A CN 104195552A CN 201410338437 A CN201410338437 A CN 201410338437A CN 104195552 A CN104195552 A CN 104195552A
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film
base
thin film
buffer layer
substrate
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CN104195552B (en
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文岐业
熊瑛
陈智
张怀武
杨青慧
田伟
毛淇
荆玉兰
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University of Electronic Science and Technology of China
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02612Formation types
    • H01L21/02617Deposition types
    • H01L21/02631Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02367Substrates
    • H01L21/0237Materials
    • H01L21/02373Group 14 semiconducting materials
    • H01L21/02381Silicon, silicon germanium, germanium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02518Deposited layers
    • H01L21/02521Materials
    • H01L21/02565Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds

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Abstract

The invention provides a method for manufacturing a high-quality VO2 thin film on a silicon base. The method aims to improve the resistance change rate of the VO2 thin film. According to the invention, the twin-polished Si base is selected. Firstly, the silicon substrate is base. Then, an Al2O3 buffer layer is formed on the Si base through deposition by the adoption of an atomic layer deposition method. Finally, a reaction magnetron sputtering method is adopted for preparing the VO2 thin film through sputtering by using the Si base with the Al2O3 buffer layer as a substrate. The method is simple in technology and easy to realize; the prepared Si-based VO2 thin film has extremely high preferred orientation and is high in quality and similar to a rutile-type VO2 film. Through the introduction of the Al2O3 buffer layer, the phase change relaxation time is reduced, and the resistance change rate is also greatly improved. The thickness of the introduced Al2O3 buffer layer is only 25 nm, so that too high threshold voltage of the Si-base VO2 thin film when the Si-base VO2 thin film acts as an electro-generated switch or an electro-generated storage device is avoided. The invention has a great significance in promoting application of the VO2 thin film in a semiconductor device.

Description

A kind of method of preparing high resistance velocity of variation vanadium dioxide film in silicon base
Technical field
The invention belongs to functional materials and thin film technique field, relate to VO 2the preparation method of film, is specially a kind of method of preparing the high resistance velocity of variation vanadium dioxide film with obvious preferred orientation in silicon base.
Background technology
Vanadium dioxide is a kind of typical metal-insulator phase transition (MIT) material, in the time of approximately 68 ℃, the reversible phase structure to Rutile Type (R phase) by monoclinic phase (M phase) occurs vanadium dioxide changes, the acute variation of simultaneous optics, electricity, magnetic performance etc.Utilize the phase transition property of this uniqueness of vanadium dioxide, make it in thermistor material, photoelectric switch material, optical storage, infrared detecting materials, the fields such as novel semi-conductor switch circuit and Terahertz modulator have a wide range of applications.Therefore, the research for vanadium dioxide film has very important scientific value.
In prior art, preparing monoclinic phase vanadium dioxide film common methods has sol-gel coating, thermal evaporation, sputtering sedimentation, pulsed laser deposition etc.Its optics of vanadium dioxide film prepared by different methods, electricity, the performances such as magnetics have very large difference.Consider the quality of economic factors, film and success ratio etc., magnetron sputtering is best suited for one of method of preparing vanadium dioxide film.
Sapphire is as a kind of substrate of typical case deposition vanadium oxide film, and itself and the perfect lattice match of monoclinic phase vanadium oxide, can realize change in resistance amplitude about four orders of magnitude at the vanadium oxide film of Grown on Sapphire Substrates.Yet, when being applied to semiconducter device, the VO growing in Si semiconducter substrate 2film is because the lattice mismatch of substrate and vanadium oxide is larger, and (Δ R) is less for sheet resistance velocity of variation, has much room for improvement.If publication number is CN1963997A, in the open day Chinese patent for 2007.05.16, a kind of Si base VO is disclosed 2the preparation technology of film, it is prepared into VO 2it is 0.06 Ω cm~10.44 Ω cm (resistance change rate is 2 orders of magnitude) that film obtains resistivity range of variation.In order to improve its resistance change rate, the mode that has scholar to propose to deposit buffer layer in Si substrate changes VO 2the quality of forming film of film.As article < < Semiconductor to metal transit ion characteristics of VO2thin films grown epitaxially on Si (001) > > (Applied Physics Let ters95,111915 (2009); Doi:10.1063/1.3232241, A.Gupta, R.Aggarwal, P.Gupta, T.Dutta, R oger, J.Narayan, andJ.Narayan) disclose a kind of YSZ that epitaxy one deck 145nm is thick on Si substrate (yttri a-stabilized zirconia) buffer layer and then deposited VO 2the method of film; VO prepared by the method 2the resistance change rate of film can reach 3 orders of magnitude.But epitaxy technique is complicated, restive, and buffer layer is thicker is easy to introduce other influences, and resistance change rate is also not ideal enough, needs further to be improved.
Summary of the invention
The object of the present invention is to provide a kind of high quality VO for preparing in silicon base 2the method of film, in order to improve silica-based VO 2thin film phase change resistance change rate and other phase-change characteristics.Technique of the present invention is simple, is easy to realize, and quality of forming film is high, is prepared into silica-based VO 2film has significantly (011) preferred orientation, and resistance change rate (Δ R) reaches 4 orders of magnitude.
Technical scheme of the present invention is: a kind of high resistance velocity of variation VO for preparing in silicon base 2the method of film, is characterized in that, comprises the following steps:
Step 1. is cleaned silicon base: select the Si substrate of twin polishing to clean up, dry up standby with nitrogen;
Step 2. depositing Al 2o 3buffer layer: adopt atomic layer deposition method (ALD) depositing Al in Si substrate 2o 3buffer layer, Si substrate is put into atomic deposition device deposit cavity, heating deposition chamber to 80~120 ℃, pass into oxygen and argon gas, control oxygen flow is 2~20sccm, argon flow amount 10~20sccm, and to keep cavity air pressure be 50~100 millitorrs, open radio frequency source switch, it is 180W that radio frequency power is set, and passes into trimethyl aluminium (TMA), deposits certain thickness Al 2o 3film; The thickness of film is more than 20nm.
VO is prepared in step 3. sputter 2film: adopt reaction magnetocontrol sputtering technology, take vanadium metal as target, take high purity oxygen gas and argon gas as reactant gases and sputter gas, be evacuated to base vacuum 2 * 10 -4~7 * 10 -4pa, passes into argon gas to operating air pressure 0.8~1.2Pa, carries out pre-sputtering, after pre-sputtering completes, passes into oxygen, and keeping oxygen partial pressure is 4~5%, to be prepared with Al through step 2 2o 3the Si substrate of buffer layer is substrate, under 450~550 ℃ of underlayer temperature conditions, carries out reactive sputtering, and sputtering power is 180~200W, and sputtering time is 20~40min, after sputter completes, closes Oxygen Flow, and cooling is prepared into Si base VO naturally 2film.
Preferably, described Si base VO 2the thickness of film is 50~250nm, is phase structure, and phase change resistor velocity of variation reaches 4 more than the order of magnitude, has (011) preferred orientation.
The present invention is by introducing Al 2o 3buffer layer, utilization is prepared sputtering method and is prepared Si base VO 2film, its advantage is:
1, adopt reaction magnetocontrol sputtering to prepare VO 2film, take vanadium metal as target, starting material environmentally safe in preparation process.
2, the VO that adopts method of the present invention to prepare 2film has extremely strong (011) preferred orientation, and quality of forming film is high, also closer to rutile-type VO 2.
3, pass through Al 2o 3the introducing of buffer layer, has reduced the phase transformation relaxation time, has also improved greatly resistance change rate (Δ R), the Si base VO that adopts method of the present invention to prepare 2its resistance change rate (Δ R) from 25 ℃ to 75 ℃ of film can reach 4 more than the order of magnitude.
4, the Al that the present invention introduces 2o 3buffer layer thickness is minimum is only 20nm, can not cause Si base VO 2film its threshold voltage when causing switch or electricity as electricity and cause memory device is excessive.
5, the present invention is to advancing VO 2the application of film in semiconducter device is significant.
Accompanying drawing explanation
Fig. 1 is that the present invention is prepared into VO 2in film and silicon base, be directly prepared into VO 2the X-ray diffraction contrast collection of illustrative plates of film.
Fig. 2 is that the present invention is prepared into VO 2in film and silicon base, be directly prepared into VO 2the atomic force microscope exterior view of film, wherein (a), (b) are respectively Si/VO 2and Si/VO 2/ Al 2o 3structure.
Fig. 3 is that the present invention is prepared into VO 2in film and silicon base, be directly prepared into VO 2the electronics surface sweeping microscope section of film, wherein (a), (b) are respectively Si/VO 2and Si/VO 2/ Al 2o 3structure.
Fig. 4 is that the present invention is prepared into VO 2in film and silicon base, be directly prepared into VO 2the normalization method sheet resistance of film varies with temperature rational curve.
Fig. 5 is that the present invention is prepared into VO 2tHz wave reflection rate change curve before and after thin film phase change.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the present invention is described in further details, it should be noted that, the present invention is not limited to this embodiment.
A kind of in silicon base preparation there is obvious preferred orientation and high resistivity velocity of variation VO 2the method of film, comprises the following steps:
First step 1. selects the Si substrate of twin polishing, then substrate is cleaned.Silicon base is put into the acid solution of self-configuring and soaked 20min, to remove surperficial organic pollutant; With the HF solution soaking silicon base 10min that uses again 25% after a large amount of deionized water rinsings, to remove the silicon oxide layer of its Surface Creation; With deionized water, rinse well again; Then use acetone ultrasonic cleaning 10min, then use alcohol ultrasonic cleaning 10min, finally use washed with de-ionized water, with nitrogen, dry up standby.
Step 2. is divided into two portions by the standby silicon base of step 1, is labeled as respectively Substrate A, B; Substrate A part is not taked any measure, and Substrate B part is at preparation VO 2first growth thickness is that the aluminum oxide film of 25nm left and right is as buffer layer before film.Aluminum oxide film using plasma strengthens atomic layer deposition system (PE-ALD) preparation, concrete grammar is as follows: take trimethyl aluminium (TMA) as aluminium source, take oxygen as reactant gases, argon gas is medium-gas, Substrate B is put into atomic deposition device deposit cavity, heating deposition chamber to 120 ℃, pass into oxygen and argon gas, control oxygen flow is 3sccm, argon flow amount 15sccm, adopt molecular pump to vacuumize simultaneously, keeping cavity air pressure is 50 millitorrs, open radio frequency source switch, it is 180W that radio frequency power is set, pass into trimethyl aluminium (TMA), deposit to obtain the thickness Al that is 25nm 2o 3buffer layer,
Step 3. is put into magnetron sputtering cavity by Substrate A, B through step 2.Adopt reactive magnetron sputtering method, take high purity oxygen gas and argon gas as reactant gases and sputter gas, first vacuum chamber is evacuated to approximately 3 * 10 -4the base vacuum of Pa, then passes into a certain amount of argon gas, makes operating air pressure in 1Pa left and right, now starts build-up of luminance, carries out pre-sputtering.After 15min, be filled with oxygen, oxygen partial pressure remains on 5% left and right, take Substrate A, B to carry out reactive sputtering as substrate under 450-550 ℃ of underlayer temperature.Sputtering power is 200W, and sputtering time is 30min; After sputter is complete, close Oxygen Flow, then naturally cool to room temperature, obtain sample Sample A (Si/VO 2structure) and Sample B (and Si/VO 2/ Al 2o 3structure).
To being prepared into sample, carry out correlation detection below:
(1) test the X ray diffracting spectrum of the prepared vanadium oxide film of the present embodiment, analyze its crystal formation; As shown in Figure 1, as seen from the figure, the present invention prepares Sample A and occurs a diffraction peak, corresponding VO in 2 θ=27.9 ° its result 2crystalline phase, the while is a ° diffraction peak of appearance in 2 θ=26.95, corresponding V 6o 13.And vanadium oxide film is typical VO in Sample B 2film, does not observe except VO 2other crystalline phases beyond crystalline phase occur, show that it is single-phase rutile-type vanadium dioxide.In addition the Si base VO that, prepared by the present invention 2film (Sample B) has extremely strong (011) preferred orientation, follows the VO depositing on sapphire 2epitaxial film is identical, shows that film has extraordinary crystal property.
(2) vanadium oxide film of being prepared by the present embodiment is by its surface grain shape of atomic force microscope observation; Its result is as shown in Figure 2. with the VO of Direct precipitation on Si base 2thin film phase change, Al 2o 3the introducing of buffer layer makes VO 2film particles shape has been transformed into sheet structure by ball-shaped.
(3) vanadium oxide film of being prepared by the present embodiment carries out its section structure of sem observation, and as shown in Figure 3, each layer film has obvious line of delimitation and layered structure clearly to its result.For Sample B, Al 2o 3thickness be 25nm, show that ALD method can obtain the film thickness needing exactly.VO 2film thickness be 204nm, show that the introducing of buffer layer does not have too much influence to its rate of film build.
(4) finally adopt the digital four point probe tester of SZ-82 to carry out resistance temperature (R-T) characteristic test to above-mentioned film, temperature range is 25 ℃ to 80 ℃, and heating unit adopts pyroelectric array semiconductor chilling plate; Its result as shown in Figure 4, the Vanadium Oxide Thin Film Resistance variation with temperature curve (R-T curve) of Grey curves for directly preparing in silicon base in Fig. 4, its phase change resistor velocity of variation approaches 3 orders of magnitude, and heat stagnation loop line width is 8 ℃, suitable with existing report; In Fig. 4, black curve is with Al 2o 3for vanadium oxide film R-T curve prepared by buffer layer, to compare with traditional technology, before and after phase transformation, its change in resistance amplitude (Δ R) has very large raising, 4 orders of magnitude have been reached, heat stagnation loop line width is reduced to 4 ℃, is significantly better than Sample A sample, with the extension VO preparing on sapphire 2film is suitable.
(5) utilize terahertz time-domain spectroscopic technology (THz-TDS) to analyze the Terahertz reflection modulation of Sample B, its result as shown in Figure 5, from figure, show before and after thin film phase change the modulation amplitude of THz wave up to 55%, can be for development THz wave regulation and control device.

Claims (2)

1. in silicon base, prepare a method for high resistance velocity of variation vanadium dioxide film, it is characterized in that, comprise the following steps:
Step 1. is cleaned silicon base: select the Si substrate of twin polishing to clean up, dry up standby with nitrogen;
Step 2. depositing Al 2o 3buffer layer: adopt atomic layer deposition method depositing Al in Si substrate 2o 3buffer layer, Si substrate is put into atomic deposition device deposit cavity, heating deposition chamber to 80~120 ℃, pass into oxygen and argon gas, control oxygen flow is 2~20sccm, argon flow amount 10~20sccm, and to keep cavity air pressure be 50~100 millitorrs, open radio frequency source switch, it is 180W that radio frequency power is set, and passes into trimethyl aluminium, deposits to obtain the thickness Al that is 20~50nm 2o 3buffer layer;
VO is prepared in step 3. sputter 2film: adopt reaction magnetocontrol sputtering technology, take vanadium metal as target, take high purity oxygen gas and argon gas as reactant gases and sputter gas, be evacuated to base vacuum 2 * 10 -4~7 * 10 -4pa, passes into argon gas to operating air pressure 0.8~1.2Pa, carries out pre-sputtering, after pre-sputtering completes, passes into oxygen, and keeping oxygen partial pressure is 4~5%, to be prepared with Al through step 2 2o 3the Si substrate of buffer layer is substrate, under 450~550 ℃ of underlayer temperature conditions, carries out reactive sputtering, and sputtering power is 180~200W, and sputtering time is 20~40min, after sputter completes, closes Oxygen Flow, and cooling is prepared into Si base VO naturally 2film.
2. by prepare the method for high resistance velocity of variation vanadium dioxide film described in claim 1 in silicon base, it is characterized in that described VO 2film growth, on semi-conductor Si, is phase structure, and film thickness is 50~250nm, and phase change resistor velocity of variation reaches 4 more than the order of magnitude, has (011) preferred orientation.
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Cited By (11)

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CN105132877A (en) * 2015-09-16 2015-12-09 深圳大学 Low-temperature deposition method for vanadium dioxide thin film
CN107487991A (en) * 2016-06-12 2017-12-19 中国科学院上海硅酸盐研究所 A kind of vanadium dioxide multilayer film and preparation method thereof
CN108070835A (en) * 2016-11-14 2018-05-25 中国科学院上海硅酸盐研究所 A kind of vanadium dioxide thin film with high temperature coefficient of resistance and its low temperature deposition method
CN109207927A (en) * 2018-11-20 2019-01-15 中国科学技术大学 A kind of preparation method of vanadium oxide monocrystal thin films
CN106011738B (en) * 2016-06-16 2019-04-09 江苏苏德涂层有限公司 A kind of mold surface plating composite coating technique
CN110128027A (en) * 2019-03-27 2019-08-16 南京工业大学 A kind of composite coating and preparation method thereof of the spontaneous temperature adjustment of multistage gradual change type
CN110736561A (en) * 2019-10-23 2020-01-31 中国科学院上海光学精密机械研究所 Preparation of reflection optical element in high-power laser system and temperature measurement method thereof
CN111133598A (en) * 2017-07-27 2020-05-08 Hrl实验室有限责任公司 Scalable and low voltage, non-cast nanoscale vanadium dioxide threshold switching device and relaxation oscillator with current controlled negative differential resistance
CN111123422A (en) * 2020-01-07 2020-05-08 南京大学 Novel terahertz dynamic adjustable grating and preparation method thereof
CN111593332A (en) * 2020-06-24 2020-08-28 湖南中大检测技术集团有限公司 Method for sputtering and depositing piezoelectric film on flexible glass
CN115125488A (en) * 2022-07-08 2022-09-30 成都市精鹰光电技术有限责任公司 Thermosensitive film prepared based on frequency mixing pulse reaction magnetron sputtering

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Cited By (18)

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Publication number Priority date Publication date Assignee Title
CN105132877A (en) * 2015-09-16 2015-12-09 深圳大学 Low-temperature deposition method for vanadium dioxide thin film
CN107487991A (en) * 2016-06-12 2017-12-19 中国科学院上海硅酸盐研究所 A kind of vanadium dioxide multilayer film and preparation method thereof
CN107487991B (en) * 2016-06-12 2019-11-15 中国科学院上海硅酸盐研究所 A kind of vanadium dioxide multilayer film and preparation method thereof
CN106011738B (en) * 2016-06-16 2019-04-09 江苏苏德涂层有限公司 A kind of mold surface plating composite coating technique
CN108070835A (en) * 2016-11-14 2018-05-25 中国科学院上海硅酸盐研究所 A kind of vanadium dioxide thin film with high temperature coefficient of resistance and its low temperature deposition method
CN108070835B (en) * 2016-11-14 2019-08-16 中国科学院上海硅酸盐研究所 A kind of vanadium dioxide thin film with high temperature coefficient of resistance and its low temperature deposition method
CN111133598A (en) * 2017-07-27 2020-05-08 Hrl实验室有限责任公司 Scalable and low voltage, non-cast nanoscale vanadium dioxide threshold switching device and relaxation oscillator with current controlled negative differential resistance
CN111133598B (en) * 2017-07-27 2023-09-12 Hrl实验室有限责任公司 Scalable and low voltage electroformless nanoscale vanadium dioxide threshold switching device and relaxation oscillator with current-controlled negative differential resistance
CN109207927A (en) * 2018-11-20 2019-01-15 中国科学技术大学 A kind of preparation method of vanadium oxide monocrystal thin films
CN109207927B (en) * 2018-11-20 2020-05-19 中国科学技术大学 Preparation method of vanadium oxide single crystal film
CN110128027B (en) * 2019-03-27 2020-12-29 南京工业大学 Multi-stage gradual-change type spontaneous temperature-adjusting composite coating and preparation method thereof
CN110128027A (en) * 2019-03-27 2019-08-16 南京工业大学 A kind of composite coating and preparation method thereof of the spontaneous temperature adjustment of multistage gradual change type
CN110736561A (en) * 2019-10-23 2020-01-31 中国科学院上海光学精密机械研究所 Preparation of reflection optical element in high-power laser system and temperature measurement method thereof
CN111123422A (en) * 2020-01-07 2020-05-08 南京大学 Novel terahertz dynamic adjustable grating and preparation method thereof
CN111593332A (en) * 2020-06-24 2020-08-28 湖南中大检测技术集团有限公司 Method for sputtering and depositing piezoelectric film on flexible glass
CN111593332B (en) * 2020-06-24 2021-06-11 湖南中大检测技术集团有限公司 Method for sputtering and depositing piezoelectric film on flexible glass
CN115125488A (en) * 2022-07-08 2022-09-30 成都市精鹰光电技术有限责任公司 Thermosensitive film prepared based on frequency mixing pulse reaction magnetron sputtering
CN115125488B (en) * 2022-07-08 2023-11-03 成都市精鹰光电技术有限责任公司 Thermosensitive film prepared based on mixed pulse reaction magnetron sputtering

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