CN102586746A - Preparation method of delafossite type copper aluminum oxide infrared transparent conductive film - Google Patents
Preparation method of delafossite type copper aluminum oxide infrared transparent conductive film Download PDFInfo
- Publication number
- CN102586746A CN102586746A CN2012100425411A CN201210042541A CN102586746A CN 102586746 A CN102586746 A CN 102586746A CN 2012100425411 A CN2012100425411 A CN 2012100425411A CN 201210042541 A CN201210042541 A CN 201210042541A CN 102586746 A CN102586746 A CN 102586746A
- Authority
- CN
- China
- Prior art keywords
- target
- preparation
- cualo
- film
- infrared transparent
- 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.)
- Pending
Links
Images
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a preparation method of a nanoscale infrared transparent conductive film, in particular to a preparation method of an infrared transparent conductive film which is used in the infrared window and is transparent and conductive. The preparation method selects sapphire or silicon (111) as a substrate material for thin film growth; the preparation method of the thin film mainly adopts a high-vacuum magnetron sputtering technology; a co-target sputtering method is provided, wherein the target materials are respectively a Cu2O target and a Al2O3 target, or a Cu target and an Al target; and the obtained thin film is annealed in nitrogen at 500-600 DEG C for 3-5h to complete a preliminary chemical reaction, and then the thin film is annealed at a high temperature of 1000-1200 DEG C for 3-5h to completely react and crystallize. According to the preparation method, by adjusting the power of the two targets to control the compositions of the thin film, the problem of the one-target sputtering method that the ratio of Cu to Al can not be accurately controlled to be 1:1 so as to generate various oxides is solved; and the two-step annealing mode is adopted to avoid the loss of the related copper oxides caused by direct high-temperature annealing, thus the quality of the thin film can be increased.
Description
Technical field
The invention belongs to infrared optical material and electric thin field of materials, be specifically related to a kind of preparation method of nano level infrared transparent conducting film, especially for the preparation method of the infrared transparent conductive film of the not only transparent but also conduction of infrared window.
Background technology
Nesa coating not only has light transmission rate but also has excellent conducting performance.Having a wide range of applications aspect FPD, touch-screen and the senser element window, but mostly present transparent conductive material is the n type; In addition; The film of using at present is only transparent in visible-range mostly; In infrared light region and opaque and have a high-reflectivity; And require to have antistatic, demist, effect such as dustproof equally in the present infrared system, therefore be necessary to prepare a kind of conducting film that good transmitance is also arranged in infrared band.
Summary of the invention
The purpose of this invention is to provide a kind of delafossite type copper alumina (CuAlO
2) preparation method of infrared transparent conductive film, (the CuAlO that the present invention is prepared
2) infrared transparent conductive film is the p type material.
According to the character matching principle, the present invention selects for use sapphire and silicon (111) as the substrate material of film growth, prepares film and mainly adopts high vacuum magnetic control sputtering technology; Propose the method for target sputter altogether, it is 99.99% Cu that target is selected purity respectively for use
2O target and purity are 99.99% Al
2O
3Target, or purity is that 99.99% Cu target and purity are 99.99% Al target; Annealing process is to make it accomplish preliminary chemical reaction at 500～650 ℃ of 3～5h that anneal down film earlier to form comparatively stable structure, makes its complete reaction and crystallization, the Al that has avoided direct high temperature annealing to cause like this at 900～1100 ℃ of 3～5h that anneal down again
2O
3And Cu
2The loss of the relevant oxide compound of the preceding copper of combination reaction takes place in O.This preparation method is through adjustment two target power outputs, and can accurately control Cu and Al mol ratio is 1: 1, and makes the multiple oxide compound that does not contain Cu and Al in the final thin film composition, thereby generates the comparatively single CuAlO of composition
2Film, thus film quality improved, transmitance is all arranged preferably and have conductivity in visible region and infrared light region.
A kind of CuAlO of the present invention
2The preparation method of infrared transparent conductive film, its step is following:
(1) cleaning of substrate:
The cleaning of silicon (111) substrate: normal temperature and pressure cleans 10～15min with acetone soln (analytical pure) down in ultrasonic cleaning machine, in HF, soak 10～15min then, uses deionized water rinsing 5～10min at last;
The cleaning of Sapphire Substrate: normal temperature and pressure cleans 10～15min with acetone soln (analytical pure) down in ultrasonic cleaning machine, use ethanolic soln (analytical pure) in ultrasonic cleaning machine, to clean 10～15min again, uses deionized water rinsing 5～10min at last,
Cleaned silicon (111) substrate and Sapphire Substrate are together put into sputtering chamber;
(2) growth for Thin Film: cathode targets is Red copper oxide Cu
2O and aluminium oxide Al
2O
3Two ceramic targets or copper and Al bimetal target, (the base vacuum degree is 0.5 * 10 at sputtering chamber
-4～2 * 10
-4Pa) the feeding volume ratio is 1: 1～1: 3 oxygen and an argon gas in, and wherein oxygen is reactant gases, and argon gas is a working gas; Vacuum is taken out the back energized and is regulated the target power supply power demand; Can produce electric field between two electrodes (wherein target position 1 is a negative electrode with target position 2 among Fig. 2, and 13 is anode among Fig. 2), when two interpolar voltages reach enough big; Promptly cause the disruptive discharge of gas; Argon gas is ionized into Ar+ and electronics, and this initiating electron e flies in the substrate process under electric field action and bumps with argon gas atmo, makes its ionization go out Ar
+With a new electronics e, Ar
+Under electromagnetic field effect, fly to the negative electrode target, and with high-energy bombardment target material surface, Ar
+Carry out energy exchange with target, thereby make target atom or molecule obtain greater than the energy of its work function sputter to take place, neutral target atom or molecule then are deposited on silicon (111) substrate or formation thickness in Sapphire Substrate surface is the CuAlO of 400nm～600nm
2Film.Target is Cu
2O and Al
2During O3 two ceramic target; The negative electrode target power supply adopts the 13.56MHz radio-frequency power supply, and power is respectively 90～110W and 140～160W, and voltage is controlled at respectively between 55～65V and the 75～85V; Anode is a ground voltage, and two electric power starting times, promptly two target co-sputtering times were 30～60min; When target was metallic target, negative electrode Cu target power supply adopted the 13.56MHz radio-frequency power supply, and negative electrode Al target power supply adopts direct supply, and power is respectively 45～55W and 70～80W, and voltage is controlled at respectively between 35～45V and the 50～60V; Anode is a ground voltage, and two electric power starting times were that two target co-sputtering times were 30～60min, and underlayer temperature remains on 180～220 ℃;
(3) aftertreatment: with the CuAlO of preparation in the step (2)
2Film is put into nitrogen together with substrate and was annealed 3～5 hours down for 500～600 ℃; Make it accomplish preliminary chemical reaction; But thin film composition reaction not exclusively and this temperature deficiency so that thin film crystallization; So continue 3～5 hours high temperature annealing time, annealing temperature is 1000～1200 ℃, thereby on substrate, prepares CuAlO
2Infrared transparent conductive film.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention adopts the high vacuum magnetic control sputtering system high quality CuAlO that grown
2Film as long as operating air pressure and sputtering power are constant, just can obtain stable deposition rate, thereby makes film comparatively uniformly.
(2) adopt Cu in the sputter procedure
2O and Al
2O
3Two ceramic targets or Cu and Al two metal targets cosputterings can be controlled the ratio of Cu and Al in the film through the power of adjusting two targets, therefore can obtain the purer CuAlO of composition
2Film.
(3) be chosen in N
2Following annealing not only guaranteed film under certain pressure intensity pyroreaction but also avoided of the pollution of other gases to film; The post processing mode of selecting to continue again behind the first medium annealing high temperature annealing makes that thin film composition is preliminary earlier chemical reaction takes place to be formed comparatively stable structure and then complete reaction and crystallization, has avoided the loss of the relevant oxide compound of copper that direct high temperature annealing causes like this.
Description of drawings
Fig. 1: CuAlO
2The preparation flow figure of film;
The preparation of film is divided into several stages, before experiment, earlier substrate is cleaned up and puts into sputtering chamber, opens the preceding elder generation of instrument and serves water coolant power-on switch then to magnetic control sputtering device, will carry on the back end vacuum and be extracted into 1.0 * 10
-4Feed sputter gas argon gas and reactant gases oxygen behind the pa, power is transferred to suitable size, the impurity of target material surface is removed in the preparatory sputter of beginning 15min, begins sputter then, after sputter is accomplished with putting into the lehre aftertreatment after the sample taking-up.
Fig. 2: CuAlO
2Film dual-target sputtering preparation facilities figure;
Each component names is: target position 1 (is Cu among the embodiment 1
2The O target is the Cu target among the embodiment 2), target position 2 (is Al among the embodiment 1
2O
3Target is the Al target among the embodiment 2), the shielding case 3 of target position 1, the shielding case 4 of target position 2, the direct supply of target position 1 or radio-frequency power supply 5; The direct supply of target position 2 or radio-frequency power supply 6 feed chilled water unit 7, vacuumometer 8, viewing window 9; Temperature regulator 10, process furnace 11, chip bench 12, anode 13; Mechanical pump 14, molecular pump 15, under meter 16, aerating oxygen and argon gas 17.
Feed water coolant 7 to magnetic control sputtering device before the start, starts power supply then, screw on shielding case 3,4 after target is put into target position 1,2 places, close the venting valve; Open mechanical pump 14, open heating temperature-controlled power 10, Heating temperature to substrate is temperature required, opens the low vacuum valve knob then; Open the digital vacuumometer 8 that shows, when the pressure demonstration is lower than 10Pa, close low vacuum valve; Open high vacuum valve, start molecular pump 15, when vacuum reaches 1.0 * 10Pa; Open argon gas and oxygen 17, regulate the desired gas flow, close high vacuum valve a little through under meter 16.Open shielding power supply 5,6, regulate matching capacitance Cl and C2 repeatedly, until build-up of luminance, regulating voltage is regulated matching capacitance C1 and C2 simultaneously and is made reflective power near 0 to power demand behind the build-up of luminance.Sputter was removed baffle plate after 15 minutes in advance earlier, and the beginning formal sputtering prepares sample.
Fig. 3: the structural representation of film;
Silicon (111) or Sapphire Substrate 18, CuAlO
2 Film 19.
Fig. 4: Cu
2O target and Al
2O
3Target spatters the CuAlO of preparation altogether
2The XRD figure of film;
Fig. 5: Cu target and Al target spatter the CuAlO of preparation altogether
2The XRD figure of film.
Fig. 4 and Fig. 5 are CuAlO
2Crystalline XRD structure iron, warp can know that with the XRD standard diagram storehouse PDF card comparison in the Search-Match software prepared film is percent crystallinity CuAlO preferably
2
Fig. 6: Cu
2O target and Al
2O
3Target spatters the CuAlO of preparation altogether
2The transmitance figure of film (square resistance is 3.5K Europe/square);
Fig. 7: Cu target and Al target spatter the CuAlO of preparation altogether
2The transmitance figure of film (square resistance is 0.22K Europe/square).
Fig. 6 and Fig. 7 are the CuAlO that records
2Film this shows the CuAlO of this kind method preparation in the transmitance of visible light and region of ultra-red
2Film can reach 70% in the region of ultra-red transmitance.
Embodiment
Embodiment 1:
(1) cleaning of substrate
The cleaning of silicon (111) substrate: normal temperature and pressure cleans 15min with acetone soln (analytical pure) down in ultrasonic cleaning machine, in HF, soak 15min then, uses deionized water rinsing 5min at last.
The cleaning of Sapphire Substrate: normal temperature and pressure cleans 15min with acetone soln (analytical pure) down in ultrasonic cleaning machine, use ethanolic soln (analytical pure) in ultrasonic cleaning machine, to clean 15min again, uses deionized water rinsing 5min at last.
With putting into sputtering chamber after two kinds of substrate oven dry, the film of wherein growing on the silicon substrate is used for the structure and the conductivity (like Fig. 4 and Fig. 5) of specimen, and the film of growing on the quartz substrate is used for the transmitance (like Fig. 6) of MEASUREMENTS OF THIN;
(2) CuAlO
2Growth for Thin Film
This process is accomplished in high vacuum multifunctional magnetic control sputtering system (like Fig. 2, wherein two targets connect radio-frequency power supply), preparation facilities such as Fig. 2, and wherein target position 1 is laid the Cu of purity 99.99%
2The O ceramic target, target position 2 is laid the Al of purity 99.99%
2O
3Ceramic target, double target co-sputtering, base vacuum are 1.0 * 10
-4Pa, O
2With Ar feeding amount be respectively 5sccm and 15sccm, wherein O
2Be reactant gases, Ar is a working gas, and electronics e bumps with ar atmo in flying to the substrate process under electric field action, makes argon gas ionization go out Ar
+With a new electronics e, argon gas ion forms Ar
+The back is the collision target under electric field action, Ar
+With the target atom exchange energy, the energy that target atom obtains will leave target material surface during greater than metallicl work function, with the reactant gases reaction and be deposited on substrate surface and form film, negative electrode Cu
2The O target uses the 13.56MHz radio-frequency power supply, and power is 100W, and voltage is 60V, negative electrode Al
2O
3Target uses 13.56MHz radio-frequency power supply power to be 150W, and voltage is 80V, and anode is a ground voltage, sputtering time 60min, and substrate keeps 200 ℃ in the sputter procedure.
(3) aftertreatment of film
The film for preparing is put into lehre anneal, feed and the isobaric N of air in the lehre
2,,, thereby obtain CuAlO of the present invention then 1100 ℃ of following high temperature annealings 4 hours earlier 600 ℃ of annealing 4 hours down
2Film.
(1) cleaning of substrate
The cleaning of silicon (111) substrate: normal temperature and pressure cleans 15min with acetone soln (analytical pure) down in ultrasonic cleaning machine, in HF, soak 15min then, uses deionized water rinsing 5min at last.
The cleaning of Sapphire Substrate: normal temperature and pressure cleans 15min with acetone soln (analytical pure) down in ultrasonic cleaning machine, use ethanolic soln (analytical pure) in ultrasonic cleaning machine, to clean 15min again, uses deionized water rinsing 5min at last.
With putting into sputtering chamber after two kinds of substrate oven dry, the film of wherein growing on the silicon substrate is used for the structure and the conductivity of specimen, and the film of growing on the quartz substrate is used for the transmitance of MEASUREMENTS OF THIN;
(2) CuAlO
2Growth for Thin Film
This process is accomplished in high vacuum multifunctional magnetic control sputtering system (like Fig. 2, wherein two targets connect direct supply), preparation facilities such as Fig. 2; Wherein target position 1 is laid the Cu metallic target of purity 99.99%; Target position 2 is laid the Al metallic target of purity 99.99%, and double target co-sputtering, base vacuum are 1.0 * 10
-4Pa, O
2With Ar feeding amount be respectively 10sccm and 10sccm, wherein O
2Be reactant gases, Ar is a working gas, and Ar ionization takes place forms Ar
+, Ar
+Collision target under electric field action, Ar
+With the target atom exchange energy, the energy that target atom obtains will leave target material surface during greater than metallicl work function, with the reactant gases reaction and be deposited on substrate surface and form film; Negative electrode Cu target uses the sputter of 13.56MHz radio-frequency power supply, and power is 50W, and voltage is 40V; Negative electrode Al target uses the direct supply sputter, and power is 70W, and voltage is 55V; Anode is a ground voltage, sputtering time 60min, and substrate remains on 200 ℃ in the sputter procedure.
(3) aftertreatment of film
The film for preparing is put into lehre anneal, feed and the isobaric N of air in the lehre
2, earlier 600 ℃ of annealing 4 hours, and then carry out high temperature annealing, annealing temperature is 1100 ℃, annealing time is 4 hours, thereby obtains CuAlO of the present invention
2Film.
Claims (7)
1. CuAlO
2The preparation method of infrared transparent conducting film, its step is following:
(1) cathode targets is Cu
2O and Al
2O
3Two ceramic targets or Cu and Al bimetal target; In sputtering chamber, feed a certain proportion of oxygen and argon gas; Wherein oxygen is reactant gases, and argon gas is a working gas, regulates the voltage between anode and cathode targets; Make target atom or molecule obtain greater than the energy of its work function thereby sputter to take place, it is the CuAlO of 400nm～600nm that neutral target atom or molecule then are deposited on substrate surface formation thickness
2Film; Underlayer temperature remains on 180～220 ℃; Cathode targets is Cu
2O and Al
2O
3During two ceramic target; Target power supply adopts the 13.56MHz radio-frequency power supply, and power is respectively 90～110W and 140～160W, and voltage is controlled at respectively between 55～65V and the 75～85V; Anode is a ground voltage, and two electric power starting times, promptly two target co-sputtering times were 30～60min; When target is the bimetal target; Negative electrode Cu target power supply adopts the 13.56MHz radio-frequency power supply; Negative electrode Al target power supply adopts direct supply, and power is respectively 45～55W and 70～80W, and voltage is controlled at respectively between 35～45V and the 50～60V; Anode is a ground voltage, and two electric power starting times, promptly two target co-sputtering times were 30～60min;
(2) will go up the CuAlO that a step prepares
2Film is put into nitrogen together with substrate and was annealed 3～5 hours down in 500～600 ℃, makes it accomplish preliminary chemical reaction, continues high temperature annealing again 3～5 hours, and annealing temperature is 1000～1200 ℃, makes to react completely and crystallization, thereby on substrate, prepares CuAlO
2Infrared transparent conductive film.
2. CuAlO as claimed in claim 1
2The preparation method of infrared transparent conducting film is characterized in that: substrate is sapphire or silicon (111).
3. CuAlO as claimed in claim 2
2The preparation method of infrared transparent conducting film is characterized in that: substrate cleans the back and uses.
4. CuAlO as claimed in claim 3
2The preparation method of infrared transparent conducting film is characterized in that: the cleaning of silicon (111) substrate is in ultrasonic cleaning machine, to clean 10～15min with acetone soln at normal temperatures and pressures, in HF, soaks 10～15min then, uses deionized water rinsing 5～10min at last.
5. CuAlO as claimed in claim 3
2The preparation method of infrared transparent conducting film; It is characterized in that: the cleaning of Sapphire Substrate: normal temperature and pressure cleans 10～15min with acetone soln down in ultrasonic cleaning machine; In ultrasonic cleaning machine, clean 10～15min with ethanolic soln again, use deionized water rinsing 5～10min at last.
6. CuAlO as claimed in claim 1
2The preparation method of infrared transparent conducting film is characterized in that: the base vacuum degree of sputtering chamber is 0.5 * 10
-4～2 * 10
-4Pa.
7. CuAlO as claimed in claim 1
2The preparation method of infrared transparent conducting film is characterized in that: the volume ratio of oxygen and argon gas is 1: 1～1: 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100425411A CN102586746A (en) | 2012-02-23 | 2012-02-23 | Preparation method of delafossite type copper aluminum oxide infrared transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100425411A CN102586746A (en) | 2012-02-23 | 2012-02-23 | Preparation method of delafossite type copper aluminum oxide infrared transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102586746A true CN102586746A (en) | 2012-07-18 |
Family
ID=46475962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100425411A Pending CN102586746A (en) | 2012-02-23 | 2012-02-23 | Preparation method of delafossite type copper aluminum oxide infrared transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102586746A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108265280A (en) * | 2018-02-13 | 2018-07-10 | 桂林理工大学 | A kind of Co/Cu2The preparation method of O nano thin-films |
| CN111969108A (en) * | 2020-08-27 | 2020-11-20 | 电子科技大学 | Flexible substrate-based copper metaaluminate memristor and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101373712A (en) * | 2008-09-11 | 2009-02-25 | 北京有色金属研究总院 | Method for preparing transparent conductive oxide CuAlO2 thin film |
| CN101752026A (en) * | 2010-01-21 | 2010-06-23 | 西北工业大学 | Infrared transparent conductive film and preparation method thereof |
-
2012
- 2012-02-23 CN CN2012100425411A patent/CN102586746A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101373712A (en) * | 2008-09-11 | 2009-02-25 | 北京有色金属研究总院 | Method for preparing transparent conductive oxide CuAlO2 thin film |
| CN101752026A (en) * | 2010-01-21 | 2010-06-23 | 西北工业大学 | Infrared transparent conductive film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| N. TSUBOI, ET. AL.: "Delafossite CuAlO2 films prepared by reactive sputtering using Cu and Al targets", 《JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108265280A (en) * | 2018-02-13 | 2018-07-10 | 桂林理工大学 | A kind of Co/Cu2The preparation method of O nano thin-films |
| CN111969108A (en) * | 2020-08-27 | 2020-11-20 | 电子科技大学 | Flexible substrate-based copper metaaluminate memristor and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4397511B2 (en) | Low resistance ITO thin film and manufacturing method thereof | |
| JP5726752B2 (en) | Transparent conductive film manufacturing method, transparent conductive film manufacturing apparatus, sputtering target, and transparent conductive film | |
| CN105565798B (en) | The preparation method of zinc oxide target and the preparation method of zinc-oxide film | |
| JP6088715B1 (en) | Substrate / orientated apatite-type composite oxide film composite and method for producing the same | |
| JP2010070410A (en) | Method for producing oxide sintered compact | |
| CN105951053B (en) | A kind of preparation method of titania-doped transparent conductive film of niobium and the titania-doped transparent conductive film of niobium | |
| CN101845614A (en) | Method for preparing zinc oxide-based sputtering target material | |
| JPWO2009044891A1 (en) | Indium oxide-based transparent conductive film and method for producing the same | |
| Bansal et al. | Growth control of molybdenum thin films with simultaneously improved adhesion and conductivity via sputtering for thin film solar cell application | |
| CN102719797A (en) | Zinc oxide based transparent conductive membrane having up-conversion function and method for preparing same | |
| CN101712549B (en) | Method for preparing lanthanum nickel oxide ceramic target | |
| CN105821379A (en) | Method for preparing single-phase transparent conductive cuprous oxide film | |
| CN102260073A (en) | Zinc-oxide-based low-voltage voltage-sensitive ceramic thin film material and preparation method thereof | |
| CN102586741B (en) | Preparation method of doped zinc oxide film | |
| CN102586746A (en) | Preparation method of delafossite type copper aluminum oxide infrared transparent conductive film | |
| JP2007246318A (en) | Oxide sintered compact, method for manufacturing the same, method for manufacturing oxide transparent conductive film, and oxide transparent conductive film | |
| CN101368258A (en) | Preparation method of negative thermal expansion material ZrW2O8 film | |
| CN1208424C (en) | Prepn of luminous tungstate film | |
| EP2921467B1 (en) | Oxide sinter, sputtering target using same, and oxide film | |
| CN102864412A (en) | Preparation method of amorphous lanthanum oxide film | |
| CN106637116A (en) | Simple preparation of secondary electron emission film | |
| CN100580843C (en) | Preparation method of MgO film to enhance the statistics of PDP on discharge delay time | |
| CN103014805A (en) | Preparation method of tough alumina ceramic membrane | |
| CN111926304B (en) | VO (volatile organic compound)2Alloy semiconductor film, preparation method and application | |
| CN110670041B (en) | Method for preparing perovskite ferroelectric film by magnetron sputtering without heat treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120718 |