CN101368258A - Preparation method of negative thermal expansion material ZrW2O8 film - Google Patents

Preparation method of negative thermal expansion material ZrW2O8 film Download PDF

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CN101368258A
CN101368258A CNA2008101569334A CN200810156933A CN101368258A CN 101368258 A CN101368258 A CN 101368258A CN A2008101569334 A CNA2008101569334 A CN A2008101569334A CN 200810156933 A CN200810156933 A CN 200810156933A CN 101368258 A CN101368258 A CN 101368258A
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程晓农
刘红飞
张志萍
杨娟
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Jiangsu University
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Abstract

The invention relates to a preparation method of a film of a negative thermal expansion material ZrW2O8, which belongs to the technical field of preparing inorganic functional film material. The method is characterized in that target material of ZrO2 and WO3 are layered and compounded in turn through a RF magnetic-control sputtering method and prepared into the film of the negative thermal expansion material ZrW2O8 through subsequent heat processing. The preparation method has the advantages of preparing the film of the negative thermal expansion material ZrW2O8 by layering and compounding the target material of ZrO2 and WO3 in turn through the RF magnetic-control sputtering method and carrying out subsequent heat processing on the target material of ZrO2 and the target material of WO3, thus effectively avoiding preferential sputtering during the sputtering process; simultaneously during the heat processing of the film, a ZrO film layer can effectively stop and avoid the volatilization of the WO3, thereby improving the purity of the film. Besides, the preparation method has excellent repeatability and is easily operated and industrialized.

Description

A kind of negative thermal expansion material ZrW 2O 8The preparation method of film
Technical field
The invention belongs to inorganic functional thin-film material preparing technical field, refer in particular to a kind of negative expansion ZrW 2O 8The preparation method of film.
Background technology
ZrW 2O 8It is one of material that has the negative expansion performance.It has three relatively more outstanding performances: than the negative expansion temperature range of broad; The negative expansion coefficient of its α phase is bigger; Has isotropy.This good characteristic both can use this negative thermal expansion material separately, also can be used to prepare matrix material, thus the coefficient of expansion of accurate control material, and its potential Application Areas has electronics, optics, microelectronics, Fiber Optical Communication System and daily life.World material scholars are with ZrW at present 2O 8Powder, pottery and relative matrix material are concentrated on the mechanism and correlated performance that discloses its related manufacturing processes, negative expansion as research object, and about negative thermal expansion material ZrW 2O 8The report of thin-film material seldom.Prepare ZrW at present 2O 8The method of film has electron-beam vapor deposition method, sol-gel processing and radio-frequency magnetron sputter method.Adopt electron beam evaporation ZrW 2O 8The method of powder prepares ZrW 2O 8Film is because evaporating course is difficult to control and WO 3Reasons such as high temperature is volatile, the thin film composition of preparation has departed from ZrW 2O 8Stoichiometric ratio; Adopt the ZrW of sol-gel coating process preparation 2O 8The preparation parameter of film is difficult to quantize, and film and substrate react in 1150 ℃ of high-temperature heat treatment process, also do not prepare pure ZrW 2O 8Film; And radio-frequency magnetron sputter method prepares film, have processing parameter be convenient to control, repeatable strong, the matrix temperature rise is low, film forming speed is fast, film component is even, film performance is stable, film adhesion strength advantages of higher, and receive much attention.Adopt single ZrO 2And WO 3The composite ceramics target, prepare ZrW with radio-frequency magnetron sputter method 2O 8Film is because ZrO 2And WO 3Different in kind, have WO in the preferential sputter of target part material and the heat treatment process 3Highly volatile causes and contains partial impurities in the film.Up to the present, still do not adopt ZrO respectively 2Target and WO 3Target, compound and after heat treatment prepare ZrW with radio-frequency magnetron sputter method stratiform successively 2O 8The report of film.
Summary of the invention
The objective of the invention is to utilize ZrO 2Target and WO 3Target, the compound and pure ZrW of employing subsequent heat treatment prepared with radio-frequency magnetron sputter method stratiform successively 2O 8Film.
A kind of negative thermal expansion material ZrW 2O 8The preparation method of film is characterized in that: adopt ZrO 2Target and WO 3Target is compound and prepare negative expansion ZrW through subsequent heat treatment with radio-frequency magnetron sputter method stratiform successively 2O 8Film.
Above-mentioned a kind of negative thermal expansion material ZrW 2O 8The preparation method of film, concrete steps are:
1, target preparation:
Respectively with ZrO 2And WO 3Be raw material, carry out ball milling behind the adding dehydrated alcohol, oven dry, adding polyvinyl alcohol (PVA) back are ground and are made it to mix, and coldmoulding, binder removal, high temperature sintering obtain ZrO respectively behind the furnace cooling 2And WO 3Target.
2, to the cleaning and the activation treatment of quartz substrate.
3, two target alternating radio frequency magnetron sputterings prepare ZrW 2O 8Film
In the rf magnetron sputtering system, with the WO of step 1 preparation 3And ZrO 2The quartz substrate that ceramic target and step 2 are cleaned is put into sputtering chamber, WO 3The preparation technology parameter of film is: radio frequency deposition power 150～280W, base vacuum degree are 2.0 * 10 -3Pa～2.0 * 10 -4Pa, operating air pressure is respectively 1～3Pa, and the distance between substrate and the target is 3～7cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 60～120min; ZrO 2The preparation technology parameter of film is: the radio frequency deposition power is 200～300W, and the base vacuum degree is 2.0 * 10 -3Pa～2.0 * 10 -4Pa, operating air pressure is respectively 1～3Pa, and the distance between substrate and the target is 3～7cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 100～240min, according to above-mentioned processing parameter, deposit WO earlier 3, deposit ZrO then 2, the composite deposition film is controlled WO by the control depositing time in the sedimentary process successively 3And ZrO 2Amount.
4, the postheat treatment of film
The base material that deposits film is taken out, quench after 3～7 minutes, can obtain pure ZrW 1150～1200 ℃ of insulations 2O 8Film.
Adopt X-ray diffractometer (XRD) that film is carried out material phase analysis; Adopt the surface topography of atomic force microscope (AFM) and scanning electronic microscope (SEM) viewing film; Thickness with surface irregularity contourgraph MEASUREMENTS OF THIN.
Among the above-mentioned preparation method, in the step 1: the ball milling time is 12～24h; The add-on of PVA accounts for ZrO 2Or WO 33～5% of quality; The pressure of coldmoulding is 80-150MPa; Dump temperature is 500 ℃, and the binder removal time is 0.5～1.5h; The high temperature sintering temperature is 1150～1200 ℃, and the high temperature sintering time is 8～12h.
Among the above-mentioned preparation method, the purging method of the quartz substrate of step 2 is: with quartz substrate at NH 3H 2O:H 2O 2: H 2Ultrasonic cleaning 10min outwells alkali lye in the solution of O=1:1:2, uses washed with de-ionized water; Again with quartz substrate at HCl:H 2O 2: H 2Ultrasonic cleaning 10min outwells acid solution in the solution of O=1:1:2, uses washed with de-ionized water.Substrate after the cleaning is immersed in the ethanol solution in order to stand-by, before substrate is sent into vacuum chamber, with high pure nitrogen substrate surface is dried up.
Among the above-mentioned preparation method, before step 3 sputter respectively to WO 3And ZrO 2Ceramic target carries out the pre-sputter of 20min, to remove the impurity and the pollutent on surface.
Among the above-mentioned preparation method, in step 3 film deposition process, on the part substrate, hide a part of substrate before the deposition, form step behind the deposit film, so that adopt the step instrument to measure its thickness with masking sheet.
Among the above-mentioned preparation method, adopt the platinum sheet airtight during the thermal treatment of step 4 film after, put into again to be heated in advance in 1150～1200 ℃ of High Temperature Furnaces Heating Apparatuss and carry out anneal.
The invention has the advantages that and utilize ZrO 2Target and WO 3Target, compound and after heat treatment prepare ZrW with radio-frequency magnetron sputter method stratiform successively 2O 8Film is effectively avoided preferential sputter, film ZrO in heat treatment process simultaneously in the sputter procedure 2Thin film layer can effectively stop and avoid WO 3Volatilization, thereby improve the purity of film.And the preparation method has good repeatability, easy handling and industrialization.
Description of drawings
Fig. 1 is stratiform combined magnetic-controlled sputter deposit film synoptic diagram successively
1, WO 32, ZrO 23, quartz substrate
Fig. 2 is stratiform combined magnetic-controlled sputter deposit film annealing back ZrW successively 2O 8The XRD figure spectrum of film
Embodiment
Raw materials usedly be: ZrO 2(analytical pure) and WO 3(analytical pure).
Adopt ZrO 2Target and WO 3Target, compound and after heat treatment prepare ZrW with radio-frequency magnetron sputter method stratiform successively 2O 8Film, the invention will be further described below in conjunction with example.
Embodiment 1
1, target preparation:
Adopt ZrO respectively 2And WO 3Be raw material, all add carry out ball milling 12h respectively behind the dehydrated alcohol after, oven dry adds PVA and grinds and make it to mix, add-on is ZrO 2Or WO 33% of quality, coldmoulding under 80MPa then.Through 500 ℃ of binder removal 0.5h,, obtain ZrO behind the furnace cooling respectively at 1150 ℃ of high temperature sintering 12h 2And WO 3Target.
2, to the cleaning and the activation treatment of quartz substrate, with quartz substrate at NH 3H 2O:H 2O 2: H 2Ultrasonic cleaning 10min outwells alkali lye in the solution of O=1:1:2, uses washed with de-ionized water; Substrate after the cleaning is immersed in the ethanol solution in order to stand-by, before substrate is sent into vacuum chamber, with high pure nitrogen substrate surface is dried up.
3, stratiform compound radio-frequency magnetron sputtering prepares ZrW 2O 8Thin-film process:
(1) in the rf magnetron sputtering system, with the WO of step 1 preparation 3And ZrO 2The quartz substrate that ceramic target and step 2 are cleaned is put into sputtering chamber, before deposit film respectively to WO 3And ZrO 2Ceramic target carries out the pre-sputter of 20min, to remove the impurity and the pollutent on surface.WO 3The preparation technology parameter of film is: radio frequency deposition power 165W, base vacuum degree are 2.0 * 10 -3Pa, operating air pressure is respectively 1.5Pa, and the distance between substrate and the target is 3cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 60min.ZrO 2The preparation technology parameter of film is: the radio frequency deposition power is 215W, and the base vacuum degree is 2.0 * 10 -3Pa, operating air pressure is respectively 1.9Pa, and the distance between substrate and the target is 3cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 100min.Measure the WO of deposition preparation under these conditions 3And ZrO 2Thickness is calculated sputter rate then and is respectively 2.95nm/min and 1.04nm/min.Because the processing parameter of magnetron sputtering deposition film can accurately be controlled, and has good repeatability,, control WO by the control depositing time according to above-mentioned processing parameter 3And ZrO 2Amount, the first WO of deposition 30min 3, deposit the ZrO of 60min then 2, composite deposition film successively.
4, the postheat treatment of film
The base material that deposits film is taken out, adopt the airtight insulation of platinum sheet to quench after 7 minutes, can obtain pure ZrW at 1150 ℃ 2O 8Film.
Embodiment 2
1, target preparation:
Adopt ZrO respectively 2And WO 3Be raw material, all add carry out ball milling 18h respectively behind the dehydrated alcohol after, oven dry adds poly-PVA and grinds and makes it to mix, add-on is ZrO 2Or WO 34% of quality, coldmoulding under 120MPa then.Through 500 ℃ of binder removal 1h,, obtain ZrO behind the furnace cooling respectively at 1180 ℃ of high temperature sintering 10h 2And WO 3Target.
2, to the cleaning and the activation treatment of quartz substrate, with quartz substrate at HCl:H 2O 2: H 2Ultrasonic cleaning 10min outwells acid solution in the solution of O=1:1:2, uses washed with de-ionized water, and the substrate after the cleaning is immersed in the ethanol solution in order to stand-by, before substrate is sent into vacuum chamber, with high pure nitrogen substrate surface is dried up.
3, stratiform compound radio-frequency magnetron sputtering prepares ZrW 2O 8Thin-film process:
(1) in the rf magnetron sputtering system, with the WO of step 1 preparation 3And ZrO 2The quartz substrate that ceramic target and step 2 are cleaned is put into sputtering chamber, before deposit film respectively to WO 3And ZrO 2Ceramic target carries out the pre-sputter of 20min, to remove the impurity and the pollutent on surface.WO 3The preparation technology parameter of film is: radio frequency deposition power 200W, base vacuum degree are 1.0 * 10 -3Pa, operating air pressure is respectively 2Pa, and the distance between substrate and the target is 3.5cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 80min.ZrO 2The preparation technology parameter of film is: the radio frequency deposition power is 230W, and the base vacuum degree is 1.0 * 10 -3Pa, operating air pressure is respectively 2.1Pa, and the distance between substrate and the target is 3.5cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 120min.Measure the WO of deposition preparation under these conditions 3And ZrO 2Thickness is calculated sputter rate 3.14nm/min and 1.55nm/min then.
(2) because the processing parameter of magnetron sputtering deposition film can accurately be controlled, have good repeatability,, deposit the WO of 30min earlier according to above-mentioned processing parameter 3, deposit the ZrO of 40min then 2, the composite deposition film is to control WO by the control depositing time in the sedimentary process successively 3And ZrO 2Amount.
4, the postheat treatment of film
The base material that deposits film is taken out, adopt the airtight insulation of platinum sheet to quench after 5 minutes, can obtain pure ZrW at 1180 ℃ 2O 8Film.
Embodiment 3
1, target preparation:
Adopt ZrO respectively 2And WO 3Be raw material, all add carry out ball milling 24h respectively behind the dehydrated alcohol after, oven dry adds PVA and grinds and make it to mix, add-on is ZrO 2Or WO 35% of quality, coldmoulding under 150MPa then.Through 500 ℃ of binder removal 1.5h,, obtain ZrO behind the furnace cooling respectively at 1200 ℃ of high temperature sintering 8h 2And WO 3Target.
2, to the cleaning and the activation treatment of quartz substrate, with quartz substrate at HCl:H 2O 2: H 2Ultrasonic cleaning 10min outwells acid solution in the solution of O=1:1:2, uses washed with de-ionized water, and the substrate after the cleaning is immersed in the ethanol solution in order to stand-by, before substrate is sent into vacuum chamber, with high pure nitrogen substrate surface is dried up.
3, stratiform compound radio-frequency magnetron sputtering prepares ZrW 2O 8Thin-film process:
(1) in the rf magnetron sputtering system, with the WO of step 1 preparation 3And ZrO 2The quartz substrate that ceramic target and step 2 are cleaned is put into sputtering chamber, before deposit film respectively to WO 3And ZrO 2Ceramic target carries out the pre-sputter of 20min, to remove the impurity and the pollutent on surface.WO 3The preparation technology parameter of film is: radio frequency deposition power 220W, base vacuum degree are 4.0 * 10 -4Pa, operating air pressure is respectively 2.2Pa, and the distance between substrate and the target is 4cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 100min.ZrO 2The preparation technology parameter of film is: the radio frequency deposition power is 250W, and the base vacuum degree is 4.0 * 10 -4Pa, operating air pressure is respectively 2.3Pa, and the distance between substrate and the target is 4cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 140min.Measure the WO of deposition preparation under these conditions 3And ZrO 2Thickness is calculated sputter rate 3.70nm/min and 1.57nm/min then.
(2) because the processing parameter of magnetron sputtering deposition film can accurately be controlled, have good repeatability,, control WO by the control depositing time according to above-mentioned processing parameter 3And ZrO 2Amount, the first WO of deposition 30min 3, deposit the ZrO of 45min then 2, composite deposition film successively.
4, the postheat treatment of film
The base material that deposits film is taken out, adopt the airtight insulation of platinum sheet to quench after 4 minutes, can obtain pure ZrW at 1200 ℃ 2O 8Film.
Three groups of case technology schemes of the present invention that table 1 provides.Prepare ZrW by the parameters such as distance, sputtering pressure, treatment temp and time that change sputtering power, target and substrate 2O 8Film.
Table 1 radio-frequency magnetron sputter method deposition WO 3And ZrO 2The experiment parameter of film
Figure A200810156933D00081
Adopt X-ray diffractometer (XRD) to carry out the material phase analysis of film, as can be seen from Figure 2, prepared synthetic film thing is zrW mutually 2O 8, together in conjunction with atomic force microscope and scanning electron microscope analysis annealed ZrW 2O 8Film is a polycrystalline film.

Claims (7)

1. negative thermal expansion material ZrW 2O 8The preparation method of film is characterized in that: adopt ZrO 2Target and WO 3Target is compound and prepare negative expansion ZrW through subsequent heat treatment with radio-frequency magnetron sputter method stratiform successively 2O 8Film.
2. the described a kind of negative thermal expansion material ZrW of claim 1 2O 8The preparation method of film is specially:
(1) target preparation:
Respectively with ZrO 2And WO 3Be raw material, carry out ball milling behind the adding dehydrated alcohol, oven dry, adding polyvinyl alcohol (PVA) back are ground and are made it to mix, and coldmoulding, binder removal, high temperature sintering obtain ZrO respectively behind the furnace cooling 2And WO 3Target;
(2) to the cleaning and the activation treatment of quartz substrate;
(3) two target alternating radio frequency magnetron sputterings prepare ZrW 2O 8Film:
In the rf magnetron sputtering system, with the WO of step 1 preparation 3And ZrO 2The quartz substrate that ceramic target and step 2 are cleaned is put into sputtering chamber, WO 3The preparation technology parameter of film is: radio frequency deposition power 150～280W, base vacuum degree are 2.0 * 10 -3Pa～2.0 * 10 -4Pa, operating air pressure is respectively 1～3Pa, and the distance between substrate and the target is 3～7cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 60～120min; ZrO 2The preparation technology parameter of film is: the radio frequency deposition power is 200～300W, and the base vacuum degree is 2.0 * 10 -3Pa～2.0 * 10 -4Pa, operating air pressure is respectively 1～3Pa, and the distance between substrate and the target is 3～7cm, and work atmosphere is V (Ar): V (O 2)=40mL/s: 8mL/s, depositing time are 100～240min, according to above-mentioned processing parameter, deposit WO earlier 3, deposit ZrO then 2, the composite deposition film is controlled WO by the control depositing time in the sedimentary process successively 3And ZrO 2Amount;
(4) postheat treatment of film:
The base material that deposits film is taken out, quench after 3～7 minutes, can obtain pure ZrW 1150～1200 ℃ of insulations 2O 8Film.
3. the described a kind of negative thermal expansion material ZrW of claim 2 2O 8The preparation method of film is characterized in that: in the step 1: the ball milling time is 12～24h; The add-on of PVA accounts for ZrO 2Or WO 33～5% of quality; The pressure of coldmoulding is 80-150MPa; Dump temperature is 500 ℃, and the binder removal time is 0.5～1.5h; The high temperature sintering temperature is 1150～1200 ℃, and the high temperature sintering time is 8～12h.
4. the described a kind of negative thermal expansion material ZrW of claim 2 2O 8The preparation method of film is characterized in that: the purging method of the quartz substrate of step 2 is: with quartz substrate at NH 3H 2O:H 2O 2: H 2Ultrasonic cleaning 10min outwells alkali lye in the solution of O=1:1:2, uses washed with de-ionized water; Again with quartz substrate at HCl:H 2O 2: H 2Ultrasonic cleaning 10min outwells acid solution in the solution of O=1:1:2, uses washed with de-ionized water.Substrate after the cleaning is immersed in the ethanol solution in order to stand-by, before substrate is sent into vacuum chamber, with high pure nitrogen substrate surface is dried up.
5. the described a kind of negative thermal expansion material ZrW of claim 2 2O 8The preparation method of film is characterized in that: before step 3 sputter respectively to WO 3And ZrO 2Ceramic target carries out the pre-sputter of 20min, to remove the impurity and the pollutent on surface.
6. the described a kind of negative thermal expansion material ZrW of claim 2 2O 8The preparation method of film is characterized in that: in step 3 film deposition process, hide a part of substrate with masking sheet before the deposition on the part substrate, form step behind the deposit film, so that adopt the step instrument to measure its thickness.
7. the described a kind of negative thermal expansion material ZrW of claim 2 2O 8The preparation method of film is characterized in that: after adopting the platinum sheet airtight during the thermal treatment of step 4 film, put into to be heated in advance in 1150～1200 ℃ of High Temperature Furnaces Heating Apparatuss again and carry out anneal.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101665361B (en) * 2009-08-25 2012-06-20 江苏大学 Method for preparing negative thermal expansion compound Fe2Mo3O12
CN103246119A (en) * 2013-05-10 2013-08-14 南京理工大学 Method for preparing tungsten trioxide (WO3) electrochromic films
CN103242846A (en) * 2012-02-10 2013-08-14 海洋王照明科技股份有限公司 Titanium phosphate luminescent film, preparation method thereof and electroluminescent device
CN103289696A (en) * 2012-02-28 2013-09-11 海洋王照明科技股份有限公司 Titanium doped lanthanum gallate luminescent material as well as preparation method and application thereof
CN103534332A (en) * 2011-06-28 2014-01-22 海洋王照明科技股份有限公司 Cerium doped magnesium barium tungstate luminescent thin film, manufacturing method and application thereof
CN106977202A (en) * 2017-04-05 2017-07-25 北京冶科纳米科技有限公司 The preparation technology and oxidation tungsten target material of a kind of High-purity low-density oxidation tungsten target material

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101665361B (en) * 2009-08-25 2012-06-20 江苏大学 Method for preparing negative thermal expansion compound Fe2Mo3O12
CN103534332A (en) * 2011-06-28 2014-01-22 海洋王照明科技股份有限公司 Cerium doped magnesium barium tungstate luminescent thin film, manufacturing method and application thereof
CN103534332B (en) * 2011-06-28 2014-12-31 海洋王照明科技股份有限公司 Cerium doped magnesium barium tungstate luminescent thin film, manufacturing method and application thereof
US9270084B2 (en) 2011-06-28 2016-02-23 Ocean's King Lighting Science & Technology Co., Ltd. Cerium doped magnesium barium tungstate luminescent thin film, manufacturing method and application thereof
CN103242846A (en) * 2012-02-10 2013-08-14 海洋王照明科技股份有限公司 Titanium phosphate luminescent film, preparation method thereof and electroluminescent device
CN103242846B (en) * 2012-02-10 2016-01-13 海洋王照明科技股份有限公司 Titanium phosphate light-emitting film, its preparation method and electroluminescent device
CN103289696A (en) * 2012-02-28 2013-09-11 海洋王照明科技股份有限公司 Titanium doped lanthanum gallate luminescent material as well as preparation method and application thereof
CN103289696B (en) * 2012-02-28 2015-07-08 海洋王照明科技股份有限公司 Titanium doped lanthanum gallate luminescent material as well as preparation method and application thereof
CN103246119A (en) * 2013-05-10 2013-08-14 南京理工大学 Method for preparing tungsten trioxide (WO3) electrochromic films
CN103246119B (en) * 2013-05-10 2015-10-14 南京理工大学 A kind of WO 3the preparation method of electrochomeric films
CN106977202A (en) * 2017-04-05 2017-07-25 北京冶科纳米科技有限公司 The preparation technology and oxidation tungsten target material of a kind of High-purity low-density oxidation tungsten target material

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