CN100424524C - Lead zirconate titanate reflection diaphragm and preparing method - Google Patents
Lead zirconate titanate reflection diaphragm and preparing method Download PDFInfo
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- CN100424524C CN100424524C CNB2004100662304A CN200410066230A CN100424524C CN 100424524 C CN100424524 C CN 100424524C CN B2004100662304 A CNB2004100662304 A CN B2004100662304A CN 200410066230 A CN200410066230 A CN 200410066230A CN 100424524 C CN100424524 C CN 100424524C
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- reflection diaphragm
- zirconate titanate
- lead zirconate
- pzt
- pbzr
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Abstract
The present invention discloses a lead zirconate titanate reflection diaphragm and a preparing method. The reflection diaphragm comprises a silicon substrate on which conductive metal oxide lanthanum nickelate buffer layers which are mutually and tightly combined are orderly arranged. Two diaphragm layers with different zirconium components are alternately arranged to form multiple periodical lead zirconate titanate reflection diaphragm stacks. The periodical lead zirconate titanate reflection diaphragm stack adopts a sol-gel method for growth, solvent is hexanediol methyl ether, a stabilizing agent is caproyl acetone, a thickening agent is polyvinylpyrrolidone, an anticracking agent is n-propanol, and solutes are lead nitrate, titanium-n-butylate and zirconium isopropoxide. The present invention has the advantages of simple used equipment, convenient operation and preparation of multilayer diaphragm series in a large area mode. Meanwhile, the central wavelength of peak value reflectivity can be controlled by means of selecting technological parameters, solution concentration, etc.
Description
Technical field
The present invention relates to a kind of reflection diaphragm of forming by multilayer dielectric film.Specifically, be a kind of by lead zirconate titanate (PZT, or molecular formula: PbZrTiO
3) the multilayer film reflection diaphragm and the preparation method that form.
Background technology
The reflectance coating of catoptron normally is made of the metal film or the interfere type multilayer dielectric film system of high reflectance in optical system.Although metal film has higher reflectivity, cannot select bandwidth of operation, simultaneously also very big by the optical energy loss that absorption causes at specific frequency band.For overcoming these restrictions, people have been developed the high reflection of dielectric multilayer composite membrane.This reflection composite membrane is generally just alternately arranged by refractive index by two kinds of materials and is formed, and the optical thickness of every tunic is 1/4th of centre wavelength.Making up the common material of compound film system has: ZnS/Na
3AlF
6(CaF
2, MgF
6), TiO
2/ SiO
2, GaAs/Al
2O
3(GaAlAs) etc.Because the PZT material has excellent a series of special performances such as electric light, piezoelectricity, acousto-optic and nonlinear optical effect, add that visible light and infrared spectral region that PZT works at most photonic device are transparent, the characteristic that its refractive index can change with the variation of process conditions, doping situation and component, and the preparation cost of pzt thin film is low, and process technology is with conventional semiconductor technology advantage such as compatibility mutually.The PZT compound has just received a large amount of concerns of scientific and technological circle since coming out.People have successfully developed various sensors, infrared eye, storer, transducer in succession, have reached various microwave devices etc. with it.PZT has become a kind of important optoelectronic functional materials.Yet the PZT material is being carried out in the past few decades of big quantity research, people never recognize the PZT multilayer film of ad hoc structure, have the character that closely absolutely reflects luminous energy at specific band.Recently, we find and first from experimentally having confirmed this key property of PZT membrane stack.We also find and can control the working band scope of film system by adjusting means such as film layer structure parameter and component simultaneously, make the one dimension membrane stack have different photon band gaps; In addition the PZT membrane stack also have wear-resistant, heat shock resistance, anti-irradiation and moisture, good chemical stability.Therefore, we recognize that this specific character of PZT membrane stack can be used for selective reflecting mirror, interference filter, optical resonator, fiber waveguide device etc.
Summary of the invention
The PZT reflection diaphragm and the preparation method that the purpose of this invention is to provide a kind of catoptron that can be used for the selectivity high reflectance, interference filter, optical resonator, fiber waveguide device.
Design of the present invention is as follows:
Because its refractive index of PZT material of different component is variant, therefore when the PZT of two kinds of different components material when the coating growth direction is alternately arranged, just form refractive index by high/low/high/low/... the 1-D photon crystal structure of distribution.By adjusting structural parameters, the component of tunic, make the PZT assembly of thin films have different forbidden photon bands, thereby obtain the high reflectance deielectric-coating of different operating frequency range.
PZT reflection diaphragm of the present invention comprises: silicon (Si) substrate 1 has the conducting metal oxide nickel acid lanthanum (LaNiO of mutual strong bonded successively on silicon chip
3) rete of 2, two kinds of different zirconium components of cushion alternately arranges the PbZrTiO that forms a plurality of cycles
3Membrane stack 3, as shown in the formula:
Si/LaNiO
3/(PbZr
xTi
1-xO
3/PbZr
yTi
1-yO
3)
n，
X, y represent the different component of Zr respectively in the formula, and satisfy the condition of 0＜x＜1,0＜y＜1, x ≠ y; N is the cycle, n=2,3,4 ..., up to required periodicity.
PZT reflection diaphragm of the present invention adopts the sol-gel process growth, and its process is as follows:
The preparation of PZT precursor solution:
Solvent is the hexanediol methyl ether, and stabilizing agent is a hexanoyl acetone, and thickening agent is a polyvinylpyrrolidone, and anti-cracking agent is a n-propanol, and their mol ratio is 28 ± 5: 0.05 ± 0.04: 1 ± 0.8: 1 ± 0.5.Solute is plumbi nitras, normal butyl alcohol titanium, zirconium iso-propoxide, and their mol ratio is respectively 1.10026 or 1.10178 or 1.10298: p: q, wherein 0＜p＜1,0＜q＜1.Earlier plumbi nitras is dissolved in the hexanediol methyl ether, successively normal butyl alcohol titanium, zirconium iso-propoxide, hexanoyl acetone, polyvinylpyrrolidone, n-propanol is added in the above-mentioned solution then, with 40-100 ℃ of water heating also agitating solution 2-3 hour.Treat to add deionized water behind the solution natural cooling, be heated to 120 ℃, byproduct of reaction is removed in distillation, and obtaining as clear as crystal concentration at last is the PZT precursor solution of 0.2-0.8mol/L.This solution underwent no deterioration in 1 year.
The preparation of PZT reflection diaphragm:
Utilize sol-gelatin plating technology, earlier the nickel acid lanthanum cushion of deposition 180-220 nanometer thickness on silicon substrate.Be the rotating speed that per minute 1000-5000 changes with whirl coating speed then, the PZT precursor solution of the X component for preparing and Y component is successively dripped on the nickel acid lanthanum cushion in the rotation, the PZT precursor solution also can drip to when sol evenning machine stops the rotation on the nickel acid lanthanum cushion, and the spin coating time of each component is 20-30 second.Then the good slice, thin piece of spin coating is put into quick anneal oven, under 180 ℃-240 ℃, 350 ℃-400 ℃ and 650 ℃-730 ℃ temperature thermal treatment 3-8 minute respectively, 3-8 minute and 5-10 minute.Repeat said process, until reaching required periodicity.
Adopt conducting metal oxide LaNiO
3As cushion, be owing to the grating constant of lead zirconate titanate with silicon is not complementary, be difficult to directly on silicon substrate, grow the flawless high-quality film of certain preferred orientation, simultaneously LaNiO
3Cushion also can be used as a hearth electrode of optoelectronic device.
Advantage of the present invention is: device therefor is simple, and is easy to operate, can the large-area preparation assembly of thin films.Simultaneously, can be by selecting technological parameter, means such as solution concentration are controlled the centre wavelength of peak reflectivity.
Description of drawings
Fig. 1 is the structural representation of PZT reflection diaphragm.
Fig. 2 is the X-ray diffractogram of (110) preferred orientation PZT multilayer film.Curve a, b, c is corresponding A respectively, B, C multilayer membrane stack.
Fig. 3 is the reflectance spectrum of multilayer membrane stack.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail:
Zirconium titanium ratio is the preparation of 30/70 solution:
The 3.6532g plumbi nitras is dissolved in the 30ml hexanediol methyl ether, again 2.1ml normal butyl alcohol titanium, 1.36ml zirconium iso-propoxide is added wherein.Add 0.5ml hexanoyl acetone subsequently successively, 0.02g polyvinylpyrrolidone, 2.11ml n-propanol, with the heating of 70 ℃ of water and agitating solution 2.5 hours, treat to add the 1.5ml deionized water behind the solution natural cooling, be heated to 120 ℃, remove a part of byproduct of reaction and solvent by distillation, obtain as clear as crystally, zirconium titanium ratio is 30/70, and volumetric molar concentration is the PZT precursor solution of 0.4mol/L.
Zirconium titanium ratio is the preparation of 40/60 solution:
The 3.6492g plumbi nitras is dissolved in the 30ml hexanediol methyl ether, again 1.8ml normal butyl alcohol titanium, 1.78ml zirconium iso-propoxide is added wherein.Add 0.3ml hexanoyl acetone subsequently successively, 0.006g polyvinylpyrrolidone, 1.45ml n-propanol, with the heating of 70 ℃ of water and agitating solution 2.5 hours, treat to add the 1.5ml deionized water behind the solution natural cooling, be heated to 120 ℃, remove a part of byproduct of reaction and solvent by distillation, obtain as clear as crystally, zirconium titanium ratio is 40/60, and volumetric molar concentration is the PZT precursor solution of 0.4mol/L.
Zirconium titanium ratio is the preparation of 50/50 solution:
The 3.6442g plumbi nitras is dissolved in the 30ml hexanediol methyl ether, again 1.5ml normal butyl alcohol titanium, 2.22ml zirconium iso-propoxide is added wherein.Add 1.5ml hexanoyl acetone subsequently successively, 0.006g polyvinylpyrrolidone, 1.2ml n-propanol, with the heating of 70 ℃ of water and agitating solution 2.5 hours, treat to add the 1.5ml deionized water behind the solution natural cooling, be heated to 120 ℃, remove a part of byproduct of reaction and solvent by distillation, obtain as clear as crystally, zirconium titanium ratio is 50/50, and volumetric molar concentration is the PZT precursor solution of 0.4mol/L.
Embodiment 4
Contain 15 periodic unit PbZr
0.5Ti
0.5O
3/ PbZr
0.4Ti
0.6O
3The preparation of multilayer membrane stack (being designated as A):
Earlier with PbZr
0.5Ti
0.5O
3Precursor solution drips to the LaNiO of silicon chip
3On the cushion, whirl coating speed is 3000 rev/mins, 30 seconds time, form gel mould, and deposit PbZr with the same terms again
0.4Ti
0.6O
3Gel mould is heat-treated subsequently, i.e. thermal treatment 3 minutes under the temperature of 200 ℃, 350 ℃ and 650 ℃ respectively, 4 minutes and 5 minutes.Repeat this step 15 time, obtain being configured as Si/LaNiO
3/ (PbZr
0.5Ti
0.5O
3/ PbZr
0.4Ti
0.6O
3)
15The multilayer membrane stack.In multilayer film, the about 81nm of the gross thickness of each cycle PZT, wherein PbZr
0.5Ti
0.5The about 42nm of the thickness of O, PbZr
0.4Ti
0.6O
3The about 39nm of thickness.Peak reflectivity is about 95%, and corresponding wavelength is 430nm, the about 28nm of forbidden photon band width.
Embodiment 5
Contain 12 periodic unit PbZr
0.5Ti
0.5O
3/ PbZr
0.3Ti
0.7O
3The preparation of multilayer membrane stack (being designated as B):
Earlier with PbZr
0.5Ti
0.5O
3Precursor solution drips to the LaNiO on the silicon chip
3On the cushion, whirl coating speed is 2500 rev/mins, 30 seconds time, forms gel mould; Deposit PbZr with the same terms again
0.3Ti
0.7O
3Gel mould, thermal treatment 4 minutes under the temperature of 180 ℃, 380 ℃ and 700 ℃ respectively subsequently, 4 minutes and 7 minutes.Repeat above-mentioned steps 12 times, obtain being configured as Si/LaNiO
3/ (PbZr
0.5Ti
0.5O
3/ PbZr
0.3Ti
0.7O
3)
12The multilayer membrane stack.In multilayer film, the about 102nm of the thickness in each PZT cycle, wherein PbZr
0.5Ti
0.5The about 54nm of the thickness of O, PbZr
0.3Ti
0.7O
3The about 48nm of thickness.Peak reflectivity is about 93%, and corresponding wavelength is 540nm, the about 40nm of forbidden photon band width.
Embodiment 6
Contain 18 periodic unit PbZr
0.4Ti
0.6O
3/ PbZr
0.3Ti
0.7O
3The preparation of assembly of thin films (being designated as C):
Earlier with PbZr
0.4Ti
0.6O
3Precursor solution drips the LaNiO that arrives on the silicon chip
3On the cushion, whirl coating speed is 2500 rev/mins, 20 seconds time, forms gel mould; Deposit PbZr with the same terms again
0.3Ti
0.7O
3Gel mould, thermal treatment 3 minutes under the temperature of 240 ℃, 400 ℃ and 720 ℃ respectively subsequently, 3 minutes and 5 minutes.Repeat this step 18 time, obtain being configured as Si/LaNiO
3/ (PbZr
0.4Ti
0.6O
3/ PbZr
0.3Ti
0.7O
3)
18The multilayer membrane stack.In multilayer film, the about 94nm of the thickness in each PZT cycle, wherein PbZr
0.4Ti
0.6The about 48nm of the thickness of O, PbZr
0.3Ti
0.7O
3The about 46nm of thickness.Peak reflectivity is about 98.6%, and corresponding wavelength is 520nm, the about 43nm of forbidden photon band width.
See accompanying drawing, in the measurement of reflectance spectrum, the reflectivity of using aluminium film is as the verification standard.We see that all membrane stacks all have very high reflectivity at specific band, and the value of reflectivity increases with the rete number, are typical 1-D photon crystal structures.The method preparation that used nickel acid lanthanum solution is all expressed according to patent document CN1362749A among the embodiment.
Claims (2)
1. lead zirconate titanate reflection diaphragm comprises: silicon chip (1), the conducting metal oxide nickel acid lanthanum cushion (2) of mutual strong bonded is arranged on silicon chip successively, and the rete of two kinds of different components is alternately arranged the PbZrTiO that forms a plurality of cycles
3Membrane stack (3), as shown in the formula:
Si/LaNiO
3/(PbZr
xTi
1-xO
3/PbZr
yTi
1-yO
3)
n，
X, y represent the different component of Zr respectively in the formula, and satisfy the condition of 0＜x＜1,0＜y＜1, x ≠ y; N is the cycle, n=2,3,4 ..., up to required periodicity.
2. one kind prepares the method for lead zirconate titanate reflection diaphragm according to claim 1, it is characterized in that concrete steps are as follows:
The preparation of A.PZT precursor solution:
Solvent is the hexanediol methyl ether, and stabilizing agent is a hexanoyl acetone, and thickening agent is a polyvinylpyrrolidone, and anti-cracking agent is a n-propanol, and their mol ratio is 28 ± 5: 0.05 ± 0.04: 1 ± 0.8: 1 ± 0.5; Solute is plumbi nitras, normal butyl alcohol titanium, zirconium iso-propoxide, and their mol ratio is respectively 1.10026 or 1.10178 or 1.10298: p: q, wherein 0＜p＜1,0＜q＜1;
Earlier plumbi nitras is dissolved in the hexanediol methyl ether, successively normal butyl alcohol titanium, zirconium iso-propoxide, hexanoyl acetone, polyvinylpyrrolidone, n-propanol are added in the above-mentioned solution then, with 40-100 ℃ of water heating also agitating solution 2-3 hour, treat to add deionized water behind the solution natural cooling, be heated to 120 ℃, byproduct of reaction is removed in distillation, and obtaining as clear as crystal concentration at last is the PZT precursor solution of 0.2-0.8mol/L;
The preparation of B.PZT reflection diaphragm:
Utilize sol-gelatin plating technology, on silicon substrate, deposit the nickel acid lanthanum cushion of 180-220 nanometer thickness earlier, be the rotating speed that per minute 1000-5000 changes with whirl coating speed then, the PZT precursor solution of two kinds of different components preparing is successively dripped on the nickel acid lanthanum cushion in the rotation, the PZT precursor solution also can drip to when sol evenning machine stops the rotation on the nickel acid lanthanum cushion, and the spin coating time of each component is 20-30 second; Subsequently the good slice, thin piece of spin coating is put into quick anneal oven, under 180 ℃-240 ℃, 350 ℃-400 ℃ and 650 ℃-730 ℃ temperature thermal treatment 3-8 minute respectively, 3-8 minute and 5-10 minute, repeat said process, until reaching required periodicity.
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100392511C (en) * | 2005-10-27 | 2008-06-04 | 中国科学院上海技术物理研究所 | Ferroelectric oxide media reflective film and process for preparing same |
| CN103626639B (en) * | 2008-10-30 | 2016-12-07 | 阿彻丹尼尔斯米德兰德公司 | With metal catalyst reduction HMF ether |
| CN112723754B (en) * | 2021-01-05 | 2023-05-05 | 聚合电光(杭州)科技有限公司 | Lead zirconate titanate film for next-generation high-speed communication and preparation method and application thereof |
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| CN1588130A (en) * | 2004-09-09 | 2005-03-02 | 中国科学院上海技术物理研究所 | Lead zirconate titanate medium reflection diaphragm and preparing method |
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2004
- 2004-09-09 CN CNB2004100662304A patent/CN100424524C/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1172723A (en) * | 1997-08-29 | 1999-03-16 | Omron Corp | Microoptical element, function element unit and their production |
| US6333066B1 (en) * | 1997-11-21 | 2001-12-25 | Samsung Electronics Co., Ltd. | Method for forming PZT thin film using seed layer |
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| US20030161601A1 (en) * | 2002-02-28 | 2003-08-28 | Ouyang Mike X. | Thin film coating process and thin film coated optical components |
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