CN101900607B - Vanadium oxide film for infrared detector and manufacturing method thereof - Google Patents
Vanadium oxide film for infrared detector and manufacturing method thereof Download PDFInfo
- Publication number
- CN101900607B CN101900607B CN201010208486XA CN201010208486A CN101900607B CN 101900607 B CN101900607 B CN 101900607B CN 201010208486X A CN201010208486X A CN 201010208486XA CN 201010208486 A CN201010208486 A CN 201010208486A CN 101900607 B CN101900607 B CN 101900607B
- Authority
- CN
- China
- Prior art keywords
- vanadium oxide
- film
- cnt
- preparation
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses a vanadium oxide film for an infrared detector and a manufacturing method thereof. The film is a vanadium oxide-carbon nanotube composite film, which is formed by compositing one-dimensional carbon nanotubes and a two-dimensional vanadium oxide film. The film is used as a thermistor material and an infrared absorption material of the infrared detector. The infrared detector is manufactured by using the vanadium oxide-carbon nanotube composite film, so that negative effect on the chemical structure of a sensitive film in the conventional manufacturing technology is overcome, shortcomings of simple carbon nanotubes or a simple vanadium oxide material in the aspects of electrical property, optical property and the like can be overcome, and the comprehensive performance of the infrared detector can be improved at the same time. The manufacturing method of the vanadium oxide-carbon nanotube composite film disclosed by the invention is simple, does not need any complex and expensive film-forming equipment, reduces manufacturing cost, improves the serviceability of the infrared detector and is suitable for massive industrial production.
Description
Technical field
The present invention relates to the uncooled ir technical field of detection, be specifically related to a kind of infrared eye thermistor material and infrared absorbing material, with and preparation method thereof.
Background technology
Infrared eye is converted into detectable electric signal to sightless infrared emanation, realizes the observation of affairs to external world.Infrared eye is divided into two types of quantum detector and thermal detectors.Thermal detector is claimed the non-refrigeration type infrared eye again, can at room temperature work, and has advantages such as the high and price of good stability, integrated level is low, has wide practical use in field such as military, commercial and civilian.Non-refrigerated infrared detector mainly comprises three types of pyroelectricity, thermopair, thermistors etc.; Wherein, Based on the micro-metering bolometer focus planardetector of thermistor, be the very swift and violent a kind of non-refrigerated infrared detector of developed recently (referring to LeonardP.Chen, " Advanced FPAs for Multiple Applications " Proc.SPIE; 4721,1-15 (2002) document).The infrared detective process of micro-metering bolometer is mainly accomplished through the micro-bridge structure that suspends, so the suspension microbridge is to influence the key factor that device is made success or failure and performance height.Micro-metering bolometer is to constructing the membraneous material of its suspension microbridge, and especially the thermistor material of device core has special requirement, is embodied in: associated materials should have performances such as suitable electricity, optics.
There is multiple material can be used as the thermistor material of infrared eye micro-metering bolometer.Wherein, vanadium oxide film has very good electricity and optical property, and the integrated level of material preparation is high, is the most frequently used high-performance non-refrigerated infrared detector thermistor material.The U.S. Pat P 5286976 that the people such as Barrett E.Cole of the Honeywll company that on February 15th, 1994 authorized declare, and document H.Jerominek, F.Picard, et al., " Micromachined, uncooled, VO
2-based, IR bolometerarrays ", Proc.SPIE, 2746,60-71 (1996) has described the infrared detector structure based on vanadium oxide thermistor film respectively.Yet, because the electronic structure of vanadium atom is 3d
34s
24s wherein and 3d track all can lose part or all of electronics; So; The preparation method of traditional vanadium oxide film, for example magnetron sputtering, electron beam evaporation, pulsed laser deposition etc. contain the shortcoming that itself can't overcome: the valence state of V element complicacy, film chemical stability of structure difference etc. in the promptly prepared vanadium oxide film.For example; When adopting magnetron sputtering to prepare vanadium oxide film; V element wherein generally comprises 0 ,+2 ,+3 ,+4 ,+multiple valence states such as 5 (referring to Xiaomei Wang, Xiangdong Xu, et al.; " Controlling the growth of VOx filmsfor various optoelectronic applications "; Proceedings of the 2009 16th IEEEInternational Symposium on the Physical and Failure Analysis of IntegratedCircuits, IPFA, p 572-576 (2009) document).Because the composition of V element is complicated, preparation technology's subtle change all can produce bigger influence to the chemical composition of vanadium oxide film, thereby makes the performance generation significant changes such as electricity, optics, mechanics of film, and then has influence on the performance of device.So based on a major defect of the infrared eye of vanadium oxide film be: preparation technology's difficulty of vanadium oxide film is big, the repeatability of product and poor stability.
The U.S. Pat P5288380 that the people such as David A.Jackson that authorized on February 22nd, 1994 declare; And the U.S. Pat P7250604 that on August 4th, 2005, the people such as Sung Mooon that authorize declared; A kind of method of cosputtering has been described, in order to improve the physical property of vanadium oxide film respectively.As sputtering target material, under certain condition, this potpourri target of sputter makes it to form gaseous component, deposits film forming then this method the vanadium oxide material that is mixed with some metallic impurity (like Ni, Fe, Cr, Mn, W etc.) in advance; Perhaps, adopt two sputtering sources splash-proofing sputtering metal and two different target sources of vanadium oxide respectively, preparation contains the vanadium oxide (VM of certain metallic impurity
xO
y, M is metallic impurity) and film, with this electric property such as resistance value, temperature-coefficient of electrical resistance, phase transition temperature of controlling vanadium oxide film, satisfy the needs of infrared eye.The shortcoming of cosputtering doping metals is: the sputter rate of metallic impurity and vanadium oxide is difficult to be consistent; So; Vanadium oxide is often also inequality with target with the ratio of metal in the film of this method preparation, and, this ratio also maybe be along with the fluctuation of sputtering technology acute variation.So the method for cosputtering is difficult to obtain the VM with fixing metering ratio, stable performance
xO
yFilm.In addition, the required equipment investment of cosputtering is big, technology is complicated.
Collosol and gel (Sol-gel) method is other a kind of method for preparing vanadium oxide film, document V.N Ovsyuk, et al., " Uncooled microbolometer IR FPA based on sol-gel VO
x", Proc.SPIE, 5834,47-54 (2005) has just described the vanadium oxide thermosensitive film that utilizes Prepared by Sol Gel Method to be used for infrared eye.The advantage of sol-gel method is that equipment is simple, and, can obtain the vanadium oxide film that valence state relatively concentrates, the effective control that helps material property.But if there is not the adjusting of other impurity, so, the resistance value of the vanadium oxide film that conventional sol-gal process obtained is bigger, and, also have phase transition phenomena under the working temperature, be unfavorable for being applied in the middle of the infrared eye.The Chinese patent 200510020789.8 that the Huang dimension of authorizing on June 13rd, 2007 has just waited the people to declare, described a kind of method that adopts the inorganic sol gel to vanadium oxide carry out metal-doped, to improve the performance of relevant vanadium oxide film.This method is at first V
2O
5With MoO
3Mix mutually, be heated under the normal pressure about 900 ℃, form fused mass; Then, pour fused mass fast in the water, add oxalic acid, NH
4F forms inorganic sol.At last, 350-500 ℃ of following annealing in process, the vanadium oxide material that obtains being mixed with Mo or W element and comprise the F element.The shortcoming of this inorganic sol gel method is: the temperature of (1) colloidal sol preparation is too high, and it is integrated to influence device; (2) comprise a large amount of nonmetal F impurity in the product, influence material property; The absorptivity of the vanadium oxide that (3) is obtained is lower, is unfavorable for the absorbing detection of infrared light.These deficiencies make the inorganic sol gel method be difficult to directly be applied in the middle of the manufacturing of infrared eye vanadium oxide thermosensitive film.
The U.S. Pat P6489613 that the people such as the Toru Mori of NEC Corporation that authorized on Dec 3rd, 2002 declare has then described other a kind of sol-gel method that improves infrared acquisition with the vanadium oxide film performance.This invention utilizes the organosol gel technique, adopts vanadium alkoxide (VO (OR)
3) as reaction raw materials; Under collosol state, in vanadium oxide, mix metallic impurity such as a certain amount of Cr, Al, Fe, Mn, Nb, Ta, Ti; Through annealing in process, the metal-doped vanadium oxide film of formation, make the resistance value of vanadium oxide, the requirement that temperature-coefficient of electrical resistance electric properties such as (TCR) meets infrared eye through the control of doping metals amount.Adopt the organosol gel method, can obtain the vanadium oxide film that valence state is relatively concentrated, the parameters such as resistance value, phase transition temperature, TCR that help film control effectively, and make it to satisfy the requirement of infrared eye.Importantly, the temperature of reaction of organosol gel method lower (＜200 ℃) helps reducing to the integrated negative effect of device.Regrettably; The organosol gel method contains some shortcomings identical with the inorganic sol gel method; Comprise: (1) on the amorphous substrate, the vanadium oxide film of the organic or attitude of polycrystalline often that the inorganic sol gel method obtains, this polycrystal film are serious to the diffuse reflectance of incident light, noise is high; So, be unfavorable for being applied directly in the infrared eye; (2) metallic impurity are that physical mixes in the prepared vanadium oxide film of organic or inorganic sol gel method; It is the effect that does not have chemical bond between itself and the vanadium oxide; So; Phenomenons such as diffusion of contaminants, segregation also take place in this film easily, cause the performance generation regression of vanadium oxide film, quality to descend, and are difficult to satisfy the long-time running needs of device; (3) the metal-doped absorbing properties that can't effectively improve vanadium oxide film that carries out of organic or inorganic sol gel method.
On the other hand, CNT is a kind of very important monodimension nanometer material.From 1991, and since the Ijima of the Japan discovery CNT (referring to Sumio Ijjima, " Helical microtubules of graphiticcarbon "; Nature, 354,56; (1991) document); Increasing research shows that this special monodimension nanometer material has the physics and the chemical property of many uniquenesses, has broad application prospects in a lot of fields.At first, CNT has very excellent chemical stability, in vacuum condition; CNT is under 1200 ℃ high temperature; It is stable that its chemical constitution can also keep, and in atmospheric environment, CNT also is being chemically stable below 650 ℃; Obviously, the chemical stability of CNT is higher than vanadium oxide film far away.In addition, CNT also has good electricity, optics, reaches mechanical property, and for example, the temperature-coefficient of electrical resistance of bibliographical information CNT (TCR) can reach 0.3～2.5%/K, and under the specified conditions, its absorption coefficient of light can reach 10
4～5Cm
-1(referring to M.E.Itkis, F.Borondics, A.Yu.R.C.Haddon; " Bolometric InfraredPhotoresponse of Suspended Single-Walled Carbon Nanotube Films "; Science, 312,413-416 (2006) document).So CNT is a kind of thermistor material with potential using value, be expected to overcome some shortcomings of traditional vanadium oxide thermosensitive film.
Summary of the invention
Problem to be solved by this invention is: how a kind of vanadium oxide film that is used for infrared eye and preparation method thereof is provided, and this film can improve working performance of devices, has reduced the raw material manufacturing cost, suitable large-scale production.
Technical matters proposed by the invention is to solve like this: a kind of preparation method who is used for the vanadium oxide film of infrared eye is provided, it is characterized in that, may further comprise the steps:
1. clean substrate, it is subsequent use to dry up the back;
2. functionalization is handled: be placed on the CNT of getting ready in advance in the beaker, adopt chemically treated mode, introduce functional group, then,, obtain functionalized carbon nanotube through filtration, washing, drying and other steps on the surface of CNT, and subsequent use;
3. vanadium oxide colloidal sol preparation: get a certain amount of vanadium oxide powder and mix mutually with organic solvent, reacting by heating, then; Through centrifuging, remove insolubles, the supernatant that extracts is left standstill; Carry out secondary centrifuging again and separate, so repeatedly, until removing insolubles fully; Obtain not have the vanadium oxide organosol of deposition, subsequent use;
4. the reaction of vanadium oxide and CNT: through step 2. the CNT of functionalization mix mutually with organic solvent; Ultrasonic dispersing Nano carbon tubes; Form the suspending liquid of CNT, then, the vanadium oxide colloidal sol that 3. prepares this carbon nano tube suspension and step mixes mutually; Dispersed with stirring forms the new colloidal sol that vanadium oxide and CNT mix mutually;
5. composite membrane preparation: be spin-coated on the substrate surface of cleaning to the step vanadium oxide that 4. prepares and the new colloidal sol that CNT mixes mutually, then,, evaporate organic solvent, formation vanadium oxide-carbon nano-tube compound film through annealing in process.
According to the preparation method who is used for the vanadium oxide film of infrared eye provided by the present invention, it is characterized in that the hybrid reaction of repeated oxidation vanadium and CNT, colloidal sol spin coating, and annealing steps form vanadium oxide-carbon nanotube multilayer structure of composite membrane successively.
According to the preparation method who is used for the vanadium oxide film of infrared eye provided by the present invention, it is characterized in that the molecular formula of vanadium oxide is expressed as VO
x, wherein, x satisfies 1.0≤x≤2.5, and the best is x=1.5,2.0,2.5.
According to the preparation method who is used for the vanadium oxide film of infrared eye provided by the present invention, it is characterized in that, step 2. in, adopt chemically treated mode to be: to adopt nitration mixture (dense H
2SO
4With dense HNO
3Mixed liquor) or red fuming nitric acid (RFNA), potassium permanganate, Fenton method processing mode in a kind of, under room temperature, heating or ultrasonic condition, CNT is handled.
According to the preparation method who is used for the vanadium oxide film of infrared eye provided by the present invention; It is characterized in that; Step 3. in, the solvent of the preparation vanadium oxide colloidal sol of employing is the mixed liquor of organic solvent A and two kinds of reagent of organic solvent B, wherein; Organic solvent A is a phenmethylol, and organic solvent B is a kind of in the middle of isobutyl alcohol or isoamylol, the isohexyl alcohol.
According to the preparation method who is used for the vanadium oxide film of infrared eye provided by the present invention; It is characterized in that; Step 3. in, the vanadium pentoxide that preparation vanadium oxide colloidal sol adopts and phenmethylol, with organic solvent A, the mol ratio that reaches three kinds of reagent of organic solvent B be vanadium pentoxide: the benzene organic solvent A: organic solvent B=1: 4: 10～1: 4: 100, wherein; Organic solvent A is a phenmethylol, and organic solvent B is a kind of in the middle of isobutyl alcohol or isoamylol, the isohexyl alcohol.
According to the preparation method who is used for the vanadium oxide film of infrared eye provided by the present invention; It is characterized in that; Step 4. in; Preparation carbon nano tube suspension used organic solvent is a kind of in the middle of isobutyl alcohol, isoamylol, the isohexyl alcohol, and the used organic solvent B of the used organic solvent of preparation carbon nano tube suspension and preparation vanadium oxide colloidal sol is consistent.
According to the preparation method who is used for the vanadium oxide film of infrared eye provided by the present invention, it is characterized in that, step 5. in, the annealing temperature of described vanadium oxide-carbon nanotube sol is 200～600 ℃, the best is 300 ℃, 350 ℃, 400 ℃, 450 ℃; Annealing atmosphere is that air, vacuum, Ar add wherein a kind of, best for to be superior to 10 in vacuum tightness such as reducibility gas
-6Carry out vacuum annealing under the condition of Torr; Annealing time is 0.5～24 hour, and the best is 1 hour, 2 hours, 3 hours, 4 hours, 5 hours.
A kind of vanadium oxide film that is used for infrared eye is characterized in that, this film is the vanadium oxide-carbon nano-tube compound film that is composited by one dimension CNT and bidimensional vanadium oxide film, as the thermistor material and the infrared absorbing material of infrared eye.What need to specify is, the exist form of CNT in composite membrane is linear structure, is referred to as the one dimension CNT, and vanadium oxide film is a membrane structure, is referred to as the bidimensional vanadium oxide film.
According to the vanadium oxide film that is used for infrared eye provided by the present invention, it is characterized in that the vanadium oxide that vanadium oxide-carbon nano-tube compound film contains is amorphous state or crystallite attitude, crystalline state nanometer, the molecular formula of vanadium oxide is expressed as VO
x, wherein, x satisfies 1.0≤x≤2.5, and the best is x=1.5,2.0,2.5.
According to the vanadium oxide film that is used for infrared eye provided by the present invention; It is characterized in that; Described one dimension CNT is dispersed in the middle of the vanadium oxide, is reticulate texture, and CNT is single wall or multi-walled carbon nano-tubes; The diameter of CNT is 1～50nm, and the best is 2nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm etc.; The length of CNT is 50～30000nm, and the best is 500nm, 800nm, 1000nm, 1200nm, 1500nm etc.; The weight content of CNT in composite membrane is 0.1～97wt.%, and the best is 1wt.%, 2wt.%, 2.5wt.%, 3wt.%, 3.5wt.%, 4wt.%, 5wt.%, 6wt.% etc.
According to the vanadium oxide film that is used for infrared eye provided by the present invention; It is characterized in that; The thickness of this composite membrane is 5～1500nm, and the best is 50nm, 100nm, 120nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm etc.; Film side's resistance of composite membrane is 1k Ω/～5M Ω/, and the best is 10k Ω/, 20k Ω/, 50k Ω/, 70k Ω/, 90k Ω/, 100k Ω/, 120k Ω/, 150k Ω/, 170k Ω/, 200k Ω/, 300k Ω/, 400k Ω/, 500k Ω/ etc.; The temperature-coefficient of electrical resistance of composite membrane (TCR) is-0.5～-4.5%/K, the best is-1.5%/K ,-1.8%/K ,-1.9%/K ,-2.0%/K ,-2.1%/K ,-2.2%/K ,-2.5%/K.
The present invention considers the specific (special) requirements of infrared eye; Simultaneously to the deficiency of the existing thermistor thin film of vanadium oxide in the device at aspects such as material property and preparation methods; A kind of method that adopts the mutually compound material of one dimension CNT and bidimensional vanadium oxide as the thermistor material and the infrared absorbing material of infrared eye is proposed; On the one hand utilize CNT excellent chemical stability, mechanical property and electric conductivity, improve the electric conductivity of conventional oxidation vanadium thermistor thin film low with shortcoming such as poor chemical stability, the negative effect of having avoided traditional doping process that vanadium oxide membrane is produced simultaneously; On the other hand; Utilize vanadium oxide high resistance, with and good temperature-coefficient of electrical resistance (TCR) and infrared Absorption performance, remedy CNT deficiency in these areas, thereby improve the combination property of device.On this basis, through regulating the ratio between vanadium oxide and the CNT, can also be more prone to, trim film performance more exactly, satisfy the special requirement of infrared eye.Utilize this infrared eye sensitive material of making by the compound substance of special monodimension nanometer material and bidimensional film, improved working performance of devices, reduced the raw material manufacturing cost, suitable large-scale industrialized production.
Description of drawings
Fig. 1 is the planimetric map of the vanadium oxide-carbon nano-tube compound film structure of embodiment of the present invention proposition;
Fig. 2 is the sectional view of the vanadium oxide-carbon nano-tube compound film structure of the individual layer that proposes of embodiment of the present invention;
Fig. 3 is the sectional view of the vanadium oxide-carbon nano-tube compound film structure of the multilayer that proposes of embodiment of the present invention;
Wherein, 1, substrate, 2, vanadium oxide-carbon nano-tube compound film, 210, the CNT in the middle of vanadium oxide-carbon nano-tube compound film, 220, the vanadium oxide in the middle of vanadium oxide-carbon nano-tube compound film.
Fig. 4 is that the film side of embodiment of the present invention preparation hinders temperature variant four-point probe measurment result: Fig. 4 (A), vanadium oxide film, Fig. 4 (B), vanadium oxide-carbon nano-tube compound film;
X-ray diffraction (XRD) measurement result: Fig. 5 (A), the vanadium oxide film of the film of the embodiment of the present invention preparation of Fig. 5 embodiment of the present invention preparation, Fig. 5 (B), vanadium oxide-carbon nano-tube compound film;
Fig. 6 is infrared spectrum (IR) measurement result of the film of embodiment of the present invention preparation: upper curve is vanadium oxide-carbon nano-tube compound film among the figure, and lower curve is a vanadium oxide film;
Fig. 7 is the vanadium oxide film of embodiment of the present invention preparation and ultraviolet-visible spectrum (UV-vis) measurement result of vanadium oxide-carbon nano-tube compound film.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described:
Guiding theory of the present invention is in vanadium oxide-carbon nano-tube compound film structure; Utilize CNT and vanadium oxide superior electrical and optical property separately; Prepare the better laminated film of combination property (as shown in Figure 1); As the thermistor material of infrared eye micro-metering bolometer, and infrared absorbing material, improve the performance (shown in Fig. 4-7) of infrared eye.Preparation vanadium oxide of the present invention-carbon nano-tube compound film embodiment is following: 1. cleans the substrate 1 of film growth, dries up with nitrogen then, and subsequent use; 2. be placed on the CNT of getting ready in advance in the beaker, adopt chemically treated method, introduce some special functional groups on the surface of CNT, then, through filtration, washing, drying and other steps.Obtain functionalized carbon nanotube, subsequent use; 3. get a certain amount of vanadium pentoxide powder and phenmethylol, and the isobutyl alcohol organic solvent mix reacting by heating mutually.Then, through centrifuging, remove insolubles.The supernatant that extracts is left standstill, carry out secondary centrifuging again and separate.So repeatedly, until removing insolubles fully.Obtain not have the vanadium oxide organosol of deposition; 4. mixing mutually with a certain amount of isobutyl alcohol organic solvent, ultrasonic dispersing Nano carbon tubes, form the isobutyl alcohol suspending liquid of CNT through the 2. CNT of functionalization; Then, mix the vanadium oxide colloidal sol of this carbon nano tube suspension mutually dispersed with stirring, the new colloidal sol that the vanadium oxide that forms solvent and be isobutyl alcohol and CNT mix mutually with 3. preparation; 5. be spin-coated on the vanadium oxide of 4. preparation and the new colloidal sol that CNT mixes mutually substrate 1 surface of cleaning.Then,, evaporate organic solvent, form vanadium oxide-carbon nano-tube compound film 2 through annealing in process; 6. as required, the hybrid reaction of repeated oxidation vanadium and CNT, colloidal sol spin coating, and step such as annealing successively, formation vanadium oxide-carbon nanotube multilayer composite membrane 2 structures; 7. after sample is cooled to room temperature, from annealing furnace, take out sample.In the middle of vanadium oxide-carbon nano-tube compound film 2, the introducing of functionalized carbon nano-tube 210 is effectively improved electricity, optical property and the steady chemical structure property etc. of vanadium oxide 220, meets the requirement of non-refrigerated infrared detector.
The concrete technology of above-mentioned preparation embodiment comprises: the preparation of (1) film growth substrate: the 650nm SiN that selects 2cm * 2cm for use
x/ Si (100) silicon chip; As the growth substrates 1 of vanadium oxide-carbon nano-tube compound film, before the experiment, clean the impurity such as greasy dirt of substrate surface earlier with washing agent; Use deionized water rinsing; Use the acetone ultrasonic cleaning then 20 minutes, and with absolute ethyl alcohol ultrasonic cleaning 20 minutes, dried up silicon chip with high pure nitrogen at last again; (2) functionalization of CNT: the mixed acid solution of the configuration 30ml concentrated sulphuric acid, 10ml red fuming nitric acid (RFNA); Taking by weighing the 0.1000g multi-walled carbon nano-tubes puts in the middle of the mixed acid solution; Mixed solution was put into ultrasonic pond (50 ℃ of temperature, 80W) sonic oscillation 3 hours; The membrane filtration of back with 0.4 μ m accomplished in reaction, and use deionized water wash filtering carbon nanotube, is 7 until the filter liquor pH value.The CNT that filtration obtains is put into 60 ℃ of baking oven bakings 24 hours; (3) preparation of vanadium oxide colloidal sol: take by weighing 2.1884g V
2O
5Mix (three's mol ratio is 1: 4: 30) with 5ml phenmethylol, 35ml isobutyl alcohol; This potpourri is put into flask; Stirring and refluxing was taken out reaction solution after 4 hours in 110 ℃ of silicone oil then; With the centrifugal 20min of the rotating speed of 2500r/min, with the filtering insolubles, take out the yellow green supernatant with hydro-extractor after centrifugal; After supernatant left standstill 1 day, centrifugal under identical centrifugal condition, further remove a small amount of remaining impurity, obtain not have the vanadium oxide organosol that precipitates; (4) reaction of vanadium oxide and CNT: take by weighing the CNT of 0.0288g, mix mutually, the suspending liquid of ultrasonic 60min (50 ℃, 70W), formation CNT with the 5ml isobutyl alcohol through (2) step function processing.Then, mix (mass percent of CNT is about 3wt.%) to the isobutyl alcohol suspending liquid of CNT mutually with 10ml vanadium oxide colloidal sol, be uniformly dispersed; (5) preparation of vanadium oxide-carbon nano-tube compound film: the new colloidal sol that the vanadium oxide of (4) step of learning from else's experience preparation and CNT mix mutually; Adopt the secondary glue spreading method of spin coating (Spin Coating) technology to carry out gluing; Technology comprises that it is 5s that 1000r/min, time are adopted in first order spin coating; It is 40s that 2500r/min, time are adopted in second level spin coating, and spin coating is four times altogether.After each spin coating, with film put into bellows be heated to 180 ℃, and insulation handle 20min, carry out spin coating next time again after to be cooled, wet gel and the film forming dissolving of last institute when preventing spin coating, form piebald.Then, prepared sample is put into muffle furnace be heated to 400 ℃ and kept one hour, carry out annealing in process, form vanadium oxide-carbon nano-tube compound film 2; (6) as required, the hybrid reaction of repeated oxidation vanadium and CNT, colloidal sol spin coating, and step such as annealing successively, formation vanadium oxide-carbon nanotube multilayer structure of composite membrane 2; (7) sampling: after (6) step, sample is cool to room temperature in muffle furnace, then, from muffle furnace, takes out sample, is vanadium oxide-carbon nano-tube compound film 2 materials that the present invention proposes.
Vanadium oxide-carbon nano-tube compound film growth substrates does not receive special restriction, except 650nm SiN
x/ Si (100) also comprises other substrate, for example the SiN of the monocrystalline silicon piece of other crystal orientation and size, other thickness
x/ Si, SiO
2/ Si, polymkeric substance (Polymer) film, glass, pottery, metal substrate etc. (different according to the substrate kind, as to adopt suitable cleaning).
The vanadium oxide film that adopts said method to process; It is the vanadium oxide-carbon nano-tube compound film that is composited by one dimension CNT and bidimensional vanadium oxide film; Thermistor material and infrared absorbing material as infrared eye; The vanadium oxide that vanadium oxide-carbon nano-tube compound film contains is amorphous state or crystallite attitude, crystalline state nanometer, and the molecular formula of vanadium oxide is expressed as VO
x, wherein, x satisfies 1.0≤x≤2.5; The best is x=1.5,2.0,2.5; The one dimension CNT is dispersed in the middle of the vanadium oxide, is reticulate texture, and CNT is single wall or multi-walled carbon nano-tubes; The diameter of CNT is 1～50nm, and the best is 2nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm etc.; The length of CNT is 50～30000nm, and the best is 500nm, 800nm, 1000nm, 1200nm, 1500nm etc.; The weight content of CNT in composite membrane is 0.1～97wt.%, and the best is 1wt.%, 2wt.%, 2.5wt.%, 3wt.%, 3.5wt.%, 4wt.%, 5wt.%, 6wt.% etc.The thickness of this composite membrane is 5～1500nm, and the best is 50nm, 100nm, 120nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm etc.; Film side's resistance of composite membrane is 1k Ω/～5M Ω/, and the best is 10k Ω/, 20k Ω/, 50k Ω/, 70k Ω/, 90k Ω/, 100k Ω/, 120k Ω/, 150k Ω/, 170k Ω/, 200k Ω/, 300k Ω/, 400k Ω/, 500k Ω/ etc.; The temperature-coefficient of electrical resistance of composite membrane (TCR) is-0.5～-4.5%/K, the best is-1.5%/K ,-1.8%/K ,-1.9%/K ,-2.0%/K ,-2.1%/KK ,-2.2%/K ,-2.5%/K.CNT in the composite membrane is the single wall or the multi-walled carbon nano-tubes of functionalization, they with vanadium oxide between combine with the mode of chemical bond, form uniform nano compound film.This complex method, making originally is the vanadium oxide that the higher vanadium oxide of crystallization degree becomes amorphous state or crystallite attitude, crystalline state nanometer, makes film more continuous, smooth, tight simultaneously; The more important thing is, sheet resistance is obviously reduced, and the corresponding enhancing of the absorbing properties of film and temperature-coefficient of electrical resistance (TCR).Adopt this vanadium oxide-carbon nano-tube compound film to be used for the making of infrared eye; Overcome the negative effect that existing manufacturing technology causes the sensitive thin film chemical constitution; Simultaneously; Can also overcome simple CNT or simple vanadium oxide material deficiency, improve the combination property of device in performances such as electricity and optics.The preparation method of vanadium oxide-carbon nano-tube compound film disclosed by the invention is simple, need not the film-forming apparatus of complicacy, costliness, has reduced manufacturing cost, has improved the serviceability of infrared eye, suitable large-scale industrialized production.
Through following methods analyst, provable employing vanadium oxide-carbon nano-tube compound film can make crystalline state, chemical constitution and resistance value, temperature-coefficient of electrical resistance (TCR), the optical property etc. of vanadium oxide that respective change takes place, and satisfies the requirement of infrared eye.
Adopt material preparation method of the present invention; The membraneous material of preparing characterizes through scanning electron microscope, and there is the crackle of a large amount of bendings in the surface that shows the vanadium oxide film that is not mixed with CNT; And by comparison; The same terms down surface ratio of the vanadium oxide-carbon nano-tube compound film of preparation is more smooth, tight, and the crackle number obviously reduces, and explains that the method for the interpolation functionalized carbon nanotube of embodiment of the present invention can improve the quality of forming film of vanadium oxide film.
Through four-point probe measurment, the result is shown in Fig. 4 (A, B) with the variation of temperature situation for sheet resistance.Fig. 4 shows that along with the rising of temperature, the thin-film electro resistance of vanadium oxide film and vanadium oxide-carbon nano-tube compound film all constantly descends; Different is, under the room temperature, side's resistance of vanadium oxide film is 936k Ω/, and the square resistance of vanadium oxide-carbon nano-tube compound film is 226k Ω/, is merely the former about 1/4; The temperature-coefficient of electrical resistance of vanadium oxide film and vanadium oxide-carbon nano-tube compound film (TCR) is respectively-2.0%/℃, and-2.1%/℃, explain that composite membrane remains unchanged even rising to some extent to the sensitivity of temperature.Fig. 4 result shows that the method for the interpolation functionalized carbon nanotube of embodiment of the present invention can be improved the electric property of vanadium oxide film significantly, makes it to meet more the requirement of infrared eye.
The X-ray diffraction of film (XRD) measurement result is as shown in Figure 5.The result shows, stronger diffraction peak appears in the vanadium oxide film of the Prepared by Sol Gel Method that 400 ℃ of annealing obtains about 8 °, 24 °, and these two peaks are corresponding V respectively
2O
5(001) and (110) crystal orientation; And (001) peak is extremely strong, explains that the crystallization degree of the vanadium oxide film that this condition prepares is higher.Yet the same terms vanadium oxide-carbon nano-tube compound film of preparation does not down have tangible XRD diffraction peak, and the adding of the CNT of functionsization has changed V
2O
5The crystal structure of film has suppressed nucleation and crystallization process, makes the higher vanadium oxide film of crystallization degree become the vanadium oxide of amorphous state or crystallite attitude, crystalline state nanometer.Our contrast experiment shows that also if interpolation is without functionalized carbon nanotube, the XRD measurement result shows; About 8 °, still can detect extremely strong diffraction peak; Explain that vanadium oxide at this moment still is the high vanadium oxide of crystallization degree, that is to say; Functionalized carbon nanotube can not change the crystal structure of vanadium oxide film, does not promptly exist strong chemical action power to be enough to influence the crystallization process of vanadium oxide between the two.So, must adopt functionalized carbon nanotube, just can make the vanadium oxide of crystalline state become amorphous vanadium oxide.
The infrared spectrum of film (IR) measurement result is as shown in Figure 6.The result shows that the prepared vanadium oxide film of embodiment of the present invention has three characteristic peaks, 507cm
-1The place is by three vanadium oxygen atom key 3V-O
CThe medium chain oxygen atom is along the flexural vibrations of a direction, 801cm
-1For the flexural vibrations peak of V-O-V, corresponding to V
5+Oxidation state, and at 1024cm
-1The absorption peak at place owing to the vibration of V=O key, be V
2O
5The eigen vibration peak.Add functionalized carbon nano-tube, form after vanadium oxide-carbon nano-tube compound film 1024cm
-1The V=O peak at place disappears, at 1424cm
-1And 1602cm
-1The place demonstrates two new peaks; 1602cm wherein
-1The peak mainly is the infrared light living features absorption of vibrations mould E by multi-walled carbon nano-tubes graphene-structured tube wall
LuProduce 1424cm
-1Absorption peak is-characteristic peak of COOH is that the O-H in-plane bending vibration by carboxyl produces.1602cm
-1The absorption peak at place shows and contains carbon nanotube molecule in the laminated film, and 1424cm
-1The new peak that the place occurs shows that CNT has chained-COOH functional group.The O atom produces hydrogen bond action in the functional group of these carbon nano tube surface and the vanadium oxide, causes that the mode with chemical bond combines between vanadium oxide and the CNT, forms fine and close, firm, stable vanadium oxide-carbon nano-tube compound film.On the other hand; The existence of these chemical bonds also changed vanadium oxide nucleation mode, suppressed the crystallization process; So, adding vanadium oxide-carbon nano-tube compound film that functionalized carbon nano-tube prepares, the crystallization degree of its vanadium oxide is lower; Be the vanadium oxide of amorphous state or crystallite attitude, crystalline state nanometer, the vanadium oxide film that does not add functionalized carbon nano-tube of preparation is obviously different down with the same terms.
The ultraviolet-visible spectrum of film (UV-vis) measurement result is as shown in Figure 7.The result shows that in the 750-1150nm wavelength coverage, the light transmission rate of vanadium oxide film is 75-65%, and the light transmission rate of vanadium oxide-carbon nano-tube compound film that the same terms prepares down is 62-55%.Explain that compare with vanadium oxide film, the absorptivity of vanadium oxide-carbon nano-tube compound film increases to some extent, increase 13-10%.So the prepared vanadium oxide-carbon nano-tube compound film of embodiment of the present invention has more superior absorbing properties.
Summary is got up; The present invention forms compound substance through the one dimension CNT that in the bidimensional vanadium oxide film, adds functionalization; Electricity, optical property and the chemical stability etc. of vanadium oxide film are effectively improved, met the needs of non-refrigerated infrared detector.With the mono-layer oxidized vanadium film of traditional independent employing or adopt CNT to compare separately as the device architecture of infrared thermistor material; The present invention adopts thermistor material and the infrared absorbing material as infrared eye based on vanadium oxide-carbon nano-tube compound film to have following advantage: (1) utilizes performances such as the good separately electricity of one dimension CNT and bidimensional vanadium oxide, optics; Obtain the better vanadium oxide of combination property-carbon nano-tube compound film material, satisfy the specific (special) requirements of non-refrigerated infrared detector; (2) through the quantitative adjusting of CNT, vanadium oxide content ratio, can be more prone to, the film performance of trim more exactly, satisfy the special requirement of infrared eye micro-metering bolometer; (3) structure of composite membrane can also obviously improve its electric property under the prerequisite that keeps the good optical property of vanadium oxide, avoids the negative effect of traditional doping process to the vanadium oxide chemical constitution simultaneously, and this is the advantage that simple vanadium oxide membrane can't possess; (4) adopt organosol gel method of the present invention to prepare vanadium oxide-carbon nano-tube compound film, low for equipment requirements, film-forming process is simple.So the vanadium oxide-carbon nano-tube compound film that obtains the present invention is used for the making of infrared eye, can overcomes existing defective in the prior art, reduce technology difficulty, improve device performance, suitable large-scale industrialized production.
Claims (9)
1. a preparation method who is used for the vanadium oxide film of infrared eye is characterized in that, may further comprise the steps:
1. clean substrate, it is subsequent use to dry up the back;
2. functionalization is handled: be placed on the CNT of getting ready in advance in the beaker, adopt chemically treated mode, introduce functional group, then,, obtain functionalized carbon nanotube through filtration, washing and drying steps on the surface of CNT, and subsequent use;
3. vanadium oxide colloidal sol preparation: the vanadium oxide powder is mixed with organic solvent mutually, reacting by heating, then; Through centrifuging, remove insolubles, the supernatant that extracts is left standstill; Carry out secondary centrifuging again and separate, so repeatedly, until removing insolubles fully; Obtain not have the vanadium oxide organosol of deposition, subsequent use;
4. the reaction of vanadium oxide and CNT: through step 2. the CNT of functionalization mix mutually with organic solvent; Ultrasonic dispersing Nano carbon tubes; Form the suspending liquid of CNT, then, the vanadium oxide colloidal sol that 3. prepares this carbon nano tube suspension and step mixes mutually; Dispersed with stirring forms the new colloidal sol that vanadium oxide and CNT mix mutually;
5. composite membrane preparation: be spin-coated on the substrate surface of cleaning to the step vanadium oxide that 4. prepares and the new colloidal sol that CNT mixes mutually, then,, evaporate organic solvent, formation vanadium oxide-carbon nano-tube compound film through annealing in process.
2. according to the said preparation method who is used for the vanadium oxide film of infrared eye of claim 1, it is characterized in that the hybrid reaction of repeated oxidation vanadium and CNT, colloidal sol spin coating, and annealing steps form vanadium oxide-carbon nanotube multilayer structure of composite membrane successively.
3. the preparation method who is used for the vanadium oxide film of infrared eye according to claim 1 is characterized in that the molecular formula of vanadium oxide is expressed as VO
x, wherein, x satisfies 1.0≤x≤2.5.
4. the preparation method who is used for the vanadium oxide film of infrared eye according to claim 1 is characterized in that, step 2. in, adopt chemically treated mode to be: to adopt dense H
2SO
4With dense HNO
3Mixed liquor, red fuming nitric acid (RFNA), potassium permanganate, Fenton method processing mode in a kind of, under room temperature, heating or ultrasonic condition, CNT is handled.
5. the preparation method who is used for the vanadium oxide film of infrared eye according to claim 1; It is characterized in that; Step 3. in, the solvent of the preparation vanadium oxide colloidal sol of employing is the mixed liquor of organic solvent A and two kinds of reagent of organic solvent B, wherein; Organic solvent A is a phenmethylol, and organic solvent B is a kind of in the middle of isobutyl alcohol or isoamylol, the isohexyl alcohol.
6. the preparation method who is used for the vanadium oxide film of infrared eye according to claim 1; It is characterized in that; Step 3. in, the vanadium pentoxide that preparation vanadium oxide colloidal sol adopts, with organic solvent A, and the mol ratio of three kinds of reagent of organic solvent B be vanadium pentoxide: organic solvent A: organic solvent B=1: 4: 10～1: 4: 100, wherein; Organic solvent A is a phenmethylol, and organic solvent B is a kind of in the middle of isobutyl alcohol or isoamylol, the isohexyl alcohol.
7. the preparation method who is used for the vanadium oxide film of infrared eye according to claim 6; It is characterized in that; Step 4. in; Preparation carbon nano tube suspension used organic solvent is a kind of in the middle of isobutyl alcohol, isoamylol, the isohexyl alcohol, and the used organic solvent B of the used organic solvent of preparation carbon nano tube suspension and preparation vanadium oxide colloidal sol is consistent.
8. the preparation method who is used for the vanadium oxide film of infrared eye according to claim 1 is characterized in that, step 5. in, the annealing temperature of described vanadium oxide-carbon nanotube sol is 200～600 ℃; Annealing atmosphere is that air, vacuum, Ar add a kind of in three kinds of atmosphere of reducibility gas; Annealing time is 0.5～24 hour.
9. according to the vanadium oxide film that is used for infrared eye of the said preparation method's gained of claim 1; It is characterized in that; This film is the vanadium oxide-carbon nano-tube compound film that is composited by one dimension CNT and bidimensional vanadium oxide film; As the thermistor material and the infrared absorbing material of infrared eye, the vanadium oxide that vanadium oxide-carbon nano-tube compound film contains is amorphous state or crystallite attitude or crystalline state nanometer, and the molecular formula of vanadium oxide is expressed as VO
x, wherein, x satisfies 1.0≤x≤2.5; The one dimension CNT is dispersed in the middle of the vanadium oxide; Be reticulate texture, CNT is single wall or multi-walled carbon nano-tubes, and the diameter of CNT is 1～50nm; The length of CNT is 50～30000nm, and the weight content of CNT in composite membrane is 0.1～97wt.%; The thickness of composite membrane is 5～1500nm; Film side's resistance of composite membrane is 1k Ω/～5M Ω/; The temperature-coefficient of electrical resistance of composite membrane is-0.5～-4.5%/K.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010208486XA CN101900607B (en) | 2010-06-24 | 2010-06-24 | Vanadium oxide film for infrared detector and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010208486XA CN101900607B (en) | 2010-06-24 | 2010-06-24 | Vanadium oxide film for infrared detector and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101900607A CN101900607A (en) | 2010-12-01 |
| CN101900607B true CN101900607B (en) | 2012-07-25 |
Family
ID=43226339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010208486XA Expired - Fee Related CN101900607B (en) | 2010-06-24 | 2010-06-24 | Vanadium oxide film for infrared detector and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101900607B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101886261B (en) * | 2010-07-09 | 2013-04-24 | 电子科技大学 | Vanadium oxide thin film for micro-metering bolometer and manufacturing method thereof |
| CN102416720B (en) * | 2011-08-17 | 2013-09-25 | 电子科技大学 | Vanadium oxide composite film and preparation method thereof |
| CN102419212B (en) * | 2011-08-18 | 2013-01-16 | 电子科技大学 | Vanadium oxide composite film and preparation method thereof |
| CN102794947B (en) * | 2012-07-25 | 2016-06-08 | 电子科技大学 | A kind of DAST-carbon nano tube composite film and preparation method thereof |
| CN104009215B (en) * | 2013-02-25 | 2016-01-27 | 张慧娟 | A kind of vanadium dioxide-graphene complex and the purposes as anode material for lithium-ion batteries thereof |
| CN104515601B (en) * | 2013-10-08 | 2017-06-27 | 黄川� | Platinum electrode negative tempperature coefficient thermistor hemisphere microballon infrared focal plane array panel |
| CN105112870B (en) * | 2015-09-14 | 2017-12-15 | 合肥芯福传感器技术有限公司 | A kind of ferroelectricity vanadium oxide composite film and preparation method thereof |
| CN105861989B (en) * | 2016-06-02 | 2018-09-28 | 中国科学院广州能源研究所 | A kind of preparation method of vanadium oxide film layer |
| CN106206830B (en) * | 2016-07-19 | 2018-07-06 | 中国科学院重庆绿色智能技术研究院 | A kind of infrared detector based on graphene interlayers formula infrared absorption layer |
| FR3077878B1 (en) * | 2018-02-15 | 2022-02-04 | Commissariat Energie Atomique | METHOD FOR MANUFACTURING A SENSITIVE MATERIAL MICROBOLOMETER BASED ON VANADIUM OXIDE |
| CN111077603B (en) * | 2019-12-30 | 2022-01-28 | 哈尔滨工业大学 | Flexible film with adjustable infrared emissivity and preparation method thereof |
| CN113235042B (en) * | 2021-05-12 | 2022-09-13 | 哈尔滨工业大学 | Anti-laser damage hybrid VO x Method for preparing phase |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1822415A (en) * | 2006-01-19 | 2006-08-23 | 同济大学 | Nano composite lithium ion cell cathode material and its preparing method |
| CN101586985A (en) * | 2008-05-23 | 2009-11-25 | 中国电子科技集团公司第十三研究所 | Integrated uncooled ir/ultraviolet two-color detector of monolithic and manufacture method thereof |
| WO2010019648A2 (en) * | 2008-08-15 | 2010-02-18 | The Regents Of The University Of California | Hierarchical nanowire composites for electrochemical energy storage |
-
2010
- 2010-06-24 CN CN201010208486XA patent/CN101900607B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1822415A (en) * | 2006-01-19 | 2006-08-23 | 同济大学 | Nano composite lithium ion cell cathode material and its preparing method |
| CN101586985A (en) * | 2008-05-23 | 2009-11-25 | 中国电子科技集团公司第十三研究所 | Integrated uncooled ir/ultraviolet two-color detector of monolithic and manufacture method thereof |
| WO2010019648A2 (en) * | 2008-08-15 | 2010-02-18 | The Regents Of The University Of California | Hierarchical nanowire composites for electrochemical energy storage |
Non-Patent Citations (1)
| Title |
|---|
| 魏雄邦.氧化钒薄膜的厚度对薄膜电学特性的影响.《材料导报》.2008,第22卷(第3期),第122-124页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101900607A (en) | 2010-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101900607B (en) | Vanadium oxide film for infrared detector and manufacturing method thereof | |
| CN102426060B (en) | Terahertz or infrared micro-bolometer and manufacturing method thereof | |
| CN101886261B (en) | Vanadium oxide thin film for micro-metering bolometer and manufacturing method thereof | |
| Shi et al. | Recent advances in fabrication strategies, phase transition modulation, and advanced applications of vanadium dioxide | |
| CN101881667B (en) | A kind of uncooled microbolometer and preparation method thereof | |
| Lehman et al. | Carbon nanotube-based black coatings | |
| Subramanian et al. | Effect of cobalt doping on the structural and optical properties of TiO2 films prepared by sol–gel process | |
| Katoch et al. | TiO2/ZnO inner/outer double-layer hollow fibers for improved detection of reducing gases | |
| CN102419212B (en) | Vanadium oxide composite film and preparation method thereof | |
| CN101774530A (en) | Microbolometer and preparation method thereof | |
| CN101915620B (en) | Preparation method of vanadium oxide thin film for microbolometer | |
| Moon et al. | A route to high sensitivity and rapid response Nb2O5-based gas sensors: TiO2 doping, surface embossing, and voltage optimization | |
| Yang et al. | Preparation of porous tin oxide nanobelts using the electrospinning technique | |
| Shi et al. | Preparation and phase transition characterization of VO 2 thin film on single crystal Si (100) substrate by sol–gel process | |
| Li et al. | Facile preparation of broadband absorbers based on patternable candle soot for applications of optical sensors | |
| Zhang et al. | Preparation and properties of VO 2 thin films by a novel sol–gel process | |
| Zhang et al. | Wafer-scale epitaxy of flexible nitride films with superior plasmonic and superconducting performance | |
| Wang et al. | Low-temperature grown vertically aligned carbon nanotube array for an optimal infrared bolometer | |
| Hao et al. | Broadband visible to mid-infrared aluminum-black absorbers and the aging behavior | |
| Sui et al. | A thin-film infrared absorber using CNT/nanodiamond nanocomposite | |
| CN102416720B (en) | Vanadium oxide composite film and preparation method thereof | |
| Zhang et al. | Controllable preparation of rGO/VO2 (B) intercalation thin films with high thermal sensitive properties | |
| Haunsbhavi et al. | Nanostructured NiO thin film for ammonia sensing at elevated temperatures | |
| Zhang et al. | Large scale synthesis of nanopyramidal-like VO2 films by an oxygen-assisted etching growth method with significantly enhanced field emission properties | |
| Mao et al. | Fabrication of nanopillar forests with high infrared absorptance based on rough poly-Si and spacer technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120725 Termination date: 20160624 |