CN105924153A - Multilayer film with sandwich structure and preparation method thereof - Google Patents

Multilayer film with sandwich structure and preparation method thereof Download PDF

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CN105924153A
CN105924153A CN201610235542.6A CN201610235542A CN105924153A CN 105924153 A CN105924153 A CN 105924153A CN 201610235542 A CN201610235542 A CN 201610235542A CN 105924153 A CN105924153 A CN 105924153A
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thin film
bst
colloidal sol
kmgbst
substrate
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廖家轩
王思哲
徐自强
吴孟强
冯婷婷
巩峰
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University of Electronic Science and Technology of China
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
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    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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Abstract

The invention discloses a multilayer film with a sandwich structure and a preparation method thereof, and belongs to the technical field of functional materials. The multilayer film comprises (2n+1) layers of films and is composed of alternatively laminated (A) films and (B) films. When the (A) films are KMgBST or BST films, the (B) films are ST films. When the (A) films are ST films, the (B) films are KMgBST or BST films. The thickness of BST films, KMgBST films, and ST films is in a range of 80 to 160 nm. Under a low bias voltage, the multilayer film has excellent comprehensive dielectric properties such as high tuning rate, low dielectric loss, and the like. Under a high bias voltage, the multilayer film has a high insulation strength and long service life. Furthermore, the ST film can provide a core position for BST film to promote the growth of film core and provide a template for the growth of next film so as to form a compact amorphous structure and good surface morphology.

Description

A kind of sandwich structure plural layers and preparation method thereof
Technical field
The invention belongs to technical field of function materials, be specifically related to a kind of BST/ST/BST (or ST/BST/ST) Plural layers of sandwich structure and preparation method thereof.
Background technology
Barium strontium titanate (BST) is as a kind of typical ferroelectric material, and its polarization intensity manifests with electric field strength Writing nonlinear change so that it is dielectric constant increases with electric field intensity and reduces, maximum during zero electric field, BST's is non- It is linearly made to demonstrate high electric tuning ability, prompt at microwave-tuned device such as voltage varactors, frequency Become the aspects such as wave filter, tuned phase shifters, variable Realtime delayer, adjustable phased array antenna to have widely Application prospect.Electric tuning ability can use tuning rate (Tunability, Tun) to describe, and is defined as Jie of zero electric field Electric constant ε0With the difference of the DIELECTRIC CONSTANT ε (E) during E field again with ε0Ratio, i.e. Tun=(ε0-ε(E))/ε0× 100%.
Electric field strength is expressed as E=V/d, and wherein, V is applied voltage or bias, and d is electric capacity the two poles of the earth Distance between plate, in the case of d is certain, V is the biggest, and Tun is the biggest, and BST electric tuning ability is the strongest, Accordingly, it would be desirable to BST has the highest breakdown voltage resistant of high dielectric strength, just to BST, especially it is thin for this Membrane structure is had higher requirement.Although the tuning rate of BST increases with bias and significantly increases, but high Bias can significantly reduce the service life of device.Much the highest Tun of Tun of the BST of report is at present The result that tens of volts the most hundreds of volt bias is lower, low bias such as 10V and within high Tun report seldom, Significantly limit the microwave-tuned application of BST material especially bst thin film.High in order to realize under low bias Dielectric constant and high tuning rate, be designed membrane structure becoming a kind of effective way with improvement.Kim J etc. (Applied physics letters, 2002,80 (19): 3581-3583) uses BaTiO3(BT)/SrTiO3(ST) alternately Structure artificial superlattice film, utilizes the distortion of lattice between monoatomic layer superlattices to create strong nonlinearity, height Dielectric constant and high tuning rate；Ortega N etc. (Journal of Applied Physics, 2013,114 (10): 104102) BT/ (Ba proposedxSr1-x)TiO3Alternating structure superlattice film has strong nonlinearity, high dielectric equally Constant and high tuning rate；Zhao N etc. (Materials Letters, 2011,65 (23): 3574-3576) are prepared for BT/BST/ST alternating structure thin film, dielectric constant and tuning rate are greatly improved.Though above-mentioned alternately superlattice structure So improve dielectric constant and tuning rate to a certain extent, but its dielectric loss is the highest.
Secondly, the many application including microwave-tuned also require that BST has low-dielectric loss, Cole M W Showing Deng research (Journal of Applied Physics, 2001,89 (11): 6336-6340), BST to be realized is thin The microwave-tuned application of film, bst thin film is except to meet such as high tuning rate, moderate dielectric constant, Low dark curient Current density, fine and close ABO3Perovskite microstructure, smooth flawless surface topography, good thermal stability Outside the performances such as film-base interface and architectural characteristic, it is most important that must have low-dielectric loss, this is to determine BST There is the prerequisite of practicality.But, owing to BST exists ferroelectricity-para-electric phase transformation, cause tuning rate and Jie Electrical loss synchronizes change, and be difficult to keep a high profile humorous rate and low-dielectric loss simultaneously, and up to the present this problem is the most not Solved very well.
Additionally, in terms of cost, integrated level and practicality, bst thin film is prepared at Pt/Ti/SiO2On/Si substrate After plate electrode on Au again to form the thin-film capacitor of Pt/BST/Au formula be most studied, the most ripe, the most real , but owing to lattice paprmeter and the thermal coefficient of expansion of BST from Pt and Au are different, at Pt/BST interface With certainly exist a certain degree of lattice mismatch on BST/Au interface, thus cause interfacial stress, affect BST The dynamic behavior of thin film and quality, the final performance deteriorating bst thin film capacitor, this problem is up till now Only it is not solved yet.
Summary of the invention
The present invention is directed to the defect that background technology exists, it is proposed that the plural layers of a kind of sandwich structure and system thereof Preparation Method.The present invention is at Pt/Ti/SiO2BST/ST/BST (KMgBST/ST/KMgBST) is formed on/Si substrate Or ST/BST/ST (ST/KMgBST/ST) sandwich structure plural layers, overcome pure BST multi-layer thin Film limitation in actual applications, plural layers of the present invention have high tuning rate under low bias and low dielectric is damaged The excellent comprehensive dielectric properties of consumption, have high dielectric strength and long service life under height biases；And this Bright middle ST layer film can provide nucleation site for bst thin film, promotes the growth of thin film forming core, for lower thin film Growth provide template, thus formed densification non crystalline structure and good surface topography.
Technical scheme is as follows:
A kind of sandwich structure plural layers, (2n+1) layer being alternatively formed including thin film A, thin film B is thin Film；When described thin film A is KMgBST or bst thin film, described thin film B is ST thin film；When described When thin film A is ST thin film, described thin film B is KMgBST or bst thin film；Described bst thin film, The thickness of KMgBST thin film and ST thin film is 80～160nm.
Further, described KMgBST is potassium and the barium strontium titanate of magnesium codope, the tool of KMgBST thin film Production procedure is: first, by soluble barium salt: solubility strontium salt: butyl titanate: polyvinylpyrrolidone =x:(1-x): the molar ratio barium strontium titanate (Ba of 1:yxSr1-xTiO3, BST) and colloidal sol, at the metatitanic acid obtained Adding soluble potassium salt precursor liquid and soluble magnesium salt precursor liquid in strontium barium colloidal sol, preparation obtains potassium magnesium codope titanium Acid strontium barium (KMgBST) colloidal sol, wherein, soluble potassium salt, solubility magnesium salt are z with the mol ratio of BST1: z2: 1；Wherein, x=0.2～0.8, y=0.5%～0.7%, z1、z2=1%～20%；Then on substrate in spin coating State KMgBST colloidal sol, drying, pyrolysis, after pre-crystallization and thermal treatment, cool down, i.e. obtain on substrate KMgBST thin film.
The preparation method of a kind of sandwich structure plural layers, comprises the following steps:
Step 1, by soluble barium salt: solubility strontium salt: butyl titanate: polyvinylpyrrolidone=x:(1-x): Molar ratio barium strontium titanate (the Ba of 1:yxSr1-xTiO3, BST) and colloidal sol, add in the barium strontium titanate colloidal sol obtained Entering soluble potassium salt precursor liquid and soluble magnesium salt precursor liquid, preparation obtains potassium magnesium codope barium strontium titanate (KMgBST) colloidal sol, wherein, soluble potassium salt, solubility magnesium salt are z with the mol ratio of BST1: z2: 1； By solubility strontium salt: the molar ratio strontium titanates (SrTiO of butyl titanate=1:13, ST) and colloidal sol；Wherein, X=0.2～0.8, y=0.5%～0.7%, z1、z2=1%～20%；
Step 2, at Pt/Ti/SiO2Spin coating KMgBST colloidal sol or ST colloidal sol on/Si substrate, drying, pyrolysis, After pre-crystallization and thermal treatment, cooling, on substrate, i.e. obtain first floor thin film (KMgBST thin film or ST thin film)；
Step 3, the process of repetition step 2, can obtain KMgBST thin film on substrate and ST thin film replaces (2n+1) layer film formed；
Step 4, (2n+1) layer film step 3 obtained carry out crystallization and thermal treatment, cooling, i.e. can get this Invent described sandwich structure plural layers.
Further, soluble barium salt described in step 1 is Barium acetate, barium nitrate, barium chloride etc..
Further, solubility strontium salt described in step 1 is strontium acetate, strontium nitrate etc..
Further, soluble potassium salt described in step 1 is potassium acetate, potassium chloride, potassium nitrate etc..
Further, solubility magnesium salt described in step 1 is magnesium acetate, magnesium chloride, magnesium nitrate etc..
Further, BST colloidal sol, KMgBST colloidal sol and ST colloidal sol described in step 1 are all to join at 70～80 DEG C System；The molar concentration of described BST colloidal sol is 0.2～0.4mol/L；Described soluble potassium salt precursor liquid and solubility The molar concentration of magnesium salt precursor liquid is 0.2～0.25mol/L；The molar concentration of ST colloidal sol is 0.15～0.2mol/L, If this concentration is more than 0.2mol/L, heating process can separate out precipitation, if this concentration can be led less than 0.15mol/L Cause thin film and crackle and hole occur, affect thin film consistency.
Further, the temperature of pre-crystallization and thermal treatment described in step 2 is 550～650 DEG C, and the time is 5～10min.
Further, the thickness of monolayer KMgBST thin film is 80～160nm, and the thickness of monolayer ST thin film is 80～160nm.
Further, the concrete preparation process of KMgBST thin film described in step 2 or ST thin film is: first will KMgBST colloidal sol or ST colloidal sol drop on substrate, the rotational speed substrate 6～8s with 3000～4000r/min, then Rotational speed substrate 30～40s with 3500～5500r/min；The most first it is placed in baking oven and is dried at 100～120 DEG C 15～20min, then in Muffle furnace, at a temperature of 300～400 DEG C, it is pyrolyzed 10～15min, finally in Muffle furnace It is incubated 5～10min at a temperature of 550～650 DEG C, carries out pre-crystallization and thermal treatment, cool to room temperature with the furnace, take out.
Further, the crystallization and thermal treatment temperature described in step 4 is 650～800 DEG C, and the time is 1～3h.
The preparation method of a kind of sandwich structure plural layers, comprises the following steps:
Step 1, by soluble barium salt: solubility strontium salt: butyl titanate: polyvinylpyrrolidone=x:(1-x): Molar ratio barium strontium titanate (the Ba of 1:yxSr1-xTiO3, BST) and colloidal sol；By solubility strontium salt: butyl titanate=1: Molar ratio strontium titanates (the SrTiO of 13, ST) and colloidal sol；Wherein, x=0.2～0.8, y=0.5%～0.7%；
Step 2, at Pt/Ti/SiO2Spin coating BST colloidal sol or ST colloidal sol on/Si substrate, drying, pyrolysis, pre-crystalline substance After heat-transformation processes, cooling, on substrate, i.e. obtain first floor thin film (bst thin film or ST thin film)；
Step 3, repeat the process of step 2, can obtain bst thin film on substrate and ST thin film is alternatively formed (2n+1) layer film；
Step 4, (2n+1) layer film step 3 obtained carry out crystallization and thermal treatment, cooling, i.e. can get this Invent described sandwich structure plural layers.
Further, soluble barium salt described in step 1 is Barium acetate, barium nitrate, barium chloride etc..
Further, solubility strontium salt described in step 1 is strontium acetate, strontium nitrate etc..
Further, BST colloidal sol described in step 1 and ST colloidal sol are all to prepare at 70～80 DEG C；Described BST is molten The molar concentration of glue is 0.2～0.4mol/L；The molar concentration of ST colloidal sol is 0.15～0.2mol/L, if this concentration More than 0.2mol/L, heating process can separate out precipitation, if this concentration can cause thin film to go out less than 0.15mol/L Existing crackle and hole, affect thin film consistency.
Further, the temperature of pre-crystallization and thermal treatment described in step 2 is 550～650 DEG C, and the time is 5～10min.
Further, the thickness of monolayer bst thin film is 80～160nm, and the thickness of monolayer ST thin film is 80～160nm.
Further, the concrete preparation process of bst thin film described in step 2 or ST thin film is: first that BST is molten Glue or ST colloidal sol drop on substrate, the rotational speed substrate 6～8s with 3000～4000r/min, then with 3500～5500 The rotational speed substrate 30～40s of r/min；The most first it is placed in baking oven at 100～120 DEG C and is dried 15～20min, then 10～15min, finally in Muffle furnace at a temperature of 550～650 DEG C it are pyrolyzed at a temperature of 300～400 DEG C in Muffle furnace Insulation 5～10min, carries out pre-crystallization and thermal treatment, cools to room temperature with the furnace, takes out.
Further, the crystallization and thermal treatment temperature described in step 4 is 650～800 DEG C, and the time is 1～3h.
The invention have the benefit that
1, the present invention is at Pt/Ti/SiO2BST/ST/BST (KMgBST/ST/KMgBST) is formed on/Si substrate Or ST/BST/ST (ST/KMgBST/ST) sandwich structure plural layers, overcome pure BST multi-layer thin Film limitation in actual applications, plural layers of the present invention have high tuning rate under low bias and low dielectric is damaged The excellent comprehensive dielectric properties of consumption, still have high dielectric strength and long service life, for reality under height biases Existing bst thin film provides material conditions and technical support in the application of microwave-tuned aspect, is also that BST is such as The otherwise application such as ferroelectricity storage, infrared acquisition, infrared array, energy storage provide material base；The present invention Middle ST layer film can provide nucleation site for BST or KMgBST thin film, promotes the growth of thin film forming core, and Pre-crystallization and thermal treatment process after spun-dried can form young crystal layer, and the growth for lower thin film provides template, Thus form the non crystalline structure of densification and good surface topography.
2, the ST room temperature in ST/BST/ST of the present invention (ST/KMgBST/ST) sandwich structure plural layers Under in paraelectric phase, be, with BST, there is the oxide of identical cubic perovskite structure, lattice paprmeter With BSTClose, and there are structure excellence, temperature stability height, insulation characterisitic height, dielectric properties The features such as excellence, under 100kHz, dielectric constant and loss are respectively 225 and 0.008, area capacitance 3.5fF/μm2, leakage current density is less than 10-8A/cm2, the crystal structure of particularly ST, lattice paprmeter, heat The coefficient of expansion (9.4ppm/K), chemical composition etc. and Pt substrate (9.0ppm/K) there is good Degree of joining, can realize the matched well with substrate；ST cushion can also provide nucleation site for bst thin film, promotees Enter the growth of thin film forming core, provide template for the growth of lower thin film, thus form fine and close non crystalline structure and good Surface topography.Therefore, ST buffer layer thin film can not only effectively solve the lattice of upper/lower electrode and bst thin film Join problem, moreover it is possible to be effectively improved the growth morphology of bst thin film, improve the consistency of thin film, improve resistance to puncturing Intensity, thus realize the high tuning rate under low bias.
3, KMgBST/ST/KMgBST of the present invention (or ST/KMgBST/ST) sandwich structure multi-layer thin KMgBST in film uses K and Mg codope BST, substitutes ABO respectively3The A position of perovskite structure Compensating doping with B position, can improve crystal structure, making thin film have, that optimizing components and structure improve is double Weight effect, effectively reduces dielectric loss.K+Ionic radius isElectronegativity is 0.82, according to tolerance The factor and elrectroneutrality pcharge-neutrality principle, during doping, K+The Ba of A position in preferential replacement bst thin film2+Ion； Mg2+Ionic radius beWith Ti4+Ionic radiusClosely, take during doping For the Ti in bst thin film4+Occupy the B position of perovskite structure, Mg2+Doping make bst thin film microcosmic tie The improvement aspect of structure and electric property has greater advantage and lifting；By K and Mg binary codope and mix The optimization of miscellaneous concentration, can effectively overcome pure BST and the shortcoming of its single doping so that it is protect under low bias Hold high tuning rate and the dielectric loss being greatly reduced, and under height biases, still there is high dielectric strength.
Accompanying drawing explanation
Fig. 1 is the structural representation of sandwich structure plural layers of the present invention；A () is embodiment 1 plural layers Structure, (b) is the structure of embodiment 2 plural layers；
Fig. 2 is the preparation flow figure of embodiment of the present invention sandwich structure plural layers；
The XRD diffracting spectrum of the thin film that Fig. 3 is embodiment 1,2 and comparative example 1,2 obtains；
Fig. 4 is the XRD diffracting spectrum of the thin film that embodiment 3-7 obtains；
The SEM figure of the thin film that Fig. 5 is comparative example 1 and embodiment 1 obtains；A () is that comparative example 1 obtains The SEM of thin film, (b) is the SEM of the thin film that embodiment 1 obtains；
The SEM figure of the thin film that Fig. 6 is embodiment 5 and embodiment 6 obtains；
(a) that the thin film that Fig. 7 is comparative example 1,2 and embodiment 1,2 obtains is tested under room temperature and 100kHz Electric capacity, (b) dielectric loss, (c) tuning rate；
Fig. 8 is the thin film that obtains of embodiment 3-6 tuning rate test curve under room temperature and 100kHz；
Fig. 9 is the thin film that obtains of embodiment 3-6 dielectric loss test curve under room temperature and 100kHz.
Figure 10 is the thin film (i.e. K2Mg2*) that obtains of embodiment 7 tuning rate under room temperature and 100kHz and Jie Electrical loss test curve.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, technical scheme is described in detail in detail.
A kind of sandwich structure plural layers, (2n+1) being alternatively formed including KMgBST thin film and ST thin film Layer film, the thickness of described KMgBST thin film and ST thin film is 80～160nm.
The preparation method of above-mentioned sandwich structure plural layers, comprises the following steps:
Step 1, by soluble barium salt: solubility strontium salt: butyl titanate: polyvinylpyrrolidone=x:(1-x): Molar ratio barium strontium titanate (the Ba of 1:yxSr1-xTiO3, BST) and colloidal sol, add in the barium strontium titanate colloidal sol obtained Entering soluble potassium salt precursor liquid and soluble magnesium salt precursor liquid, preparation obtains potassium magnesium codope barium strontium titanate (KMgBST) colloidal sol, wherein, soluble potassium salt, solubility magnesium salt are z with the mol ratio of BST1: z2: 1； By solubility strontium salt: the molar ratio strontium titanates (SrTiO of butyl titanate=1:13, ST) and colloidal sol；Wherein, X=0.2～0.8, y=0.5%～0.7%, z1、z2The molar concentration of=1%～20%, BST colloidal sol is 0.2～0.4mol/L, The molar concentration of soluble potassium salt precursor liquid and soluble magnesium salt precursor liquid is 0.2～0.25mol/L, ST colloidal sol Molar concentration is 0.15～0.2mol/L；
Step 2, at Pt/Ti/SiO2Spin coating KMgBST colloidal sol or ST colloidal sol on the Pt of/Si substrate, with 3000～4000 The rotational speed substrate 6～8s of r/min, then the rotational speed substrate 30～40s with 3500～5500r/min；Then first It is placed in baking oven and at 100～120 DEG C, is dried 15～20min, after taking-up, be positioned in Muffle furnace, with 10～15 DEG C/min Heating rate be warming up to 300～400 DEG C, at a temperature of 300～400 DEG C be pyrolyzed 10～15min, finally with The heating rate of 10～15 DEG C/min is warming up to 550～650 DEG C, is incubated 5～10min at a temperature of 550～650 DEG C, Carry out pre-crystallization and thermal treatment, cool to room temperature with the furnace, take out, on substrate, i.e. obtain first floor thin film (KMgBST Thin film or ST thin film)；
Step 3, the process of repetition step 2, can obtain KMgBST thin film on substrate and ST thin film replaces (2n+1) layer film formed；
Step 4, the substrate of band (2n+1) layer film step 3 obtained are positioned in Muffle furnace, at 650～800 DEG C At a temperature of be incubated 1～3h, carry out crystallization and thermal treatment, cooling, i.e. can get sandwich structure multilamellar of the present invention Thin film.
A kind of sandwich structure plural layers, (2n+1) layer being alternatively formed including bst thin film and ST thin film Thin film, the thickness of described bst thin film and ST thin film is 80～160nm.
The preparation method of above-mentioned sandwich structure plural layers, comprises the following steps:
Step 1, by soluble barium salt: solubility strontium salt: butyl titanate: polyvinylpyrrolidone=x:(1-x): Molar ratio barium strontium titanate (the Ba of 1:yxSr1-xTiO3, BST) and colloidal sol；By solubility strontium salt: butyl titanate=1: Molar ratio strontium titanates (the SrTiO of 13, ST) and colloidal sol；Wherein, x=0.2～0.8, y=0.5%～0.7%, BST The molar concentration of colloidal sol is 0.2～0.4mol/L, and the molar concentration of ST colloidal sol is 0.15～0.2mol/L；
Step 2, at Pt/Ti/SiO2Spin coating BST colloidal sol or ST colloidal sol on the Pt of/Si substrate, with 3000～4000r/min Rotational speed substrate 6～8s, then the rotational speed substrate 30～40s with 3500～5500r/min；The most first it is placed in Baking oven is dried at 100～120 DEG C 15～20min, after taking-up, is positioned in Muffle furnace, with 10～15 DEG C/min Heating rate be warming up to 300～400 DEG C, at a temperature of 300～400 DEG C be pyrolyzed 10～15min, finally with The heating rate of 10～15 DEG C/min is warming up to 550～650 DEG C, is incubated 5～10min at a temperature of 550～650 DEG C, Carrying out pre-crystallization and thermal treatment, cool to room temperature with the furnace, take out, (BST is thin i.e. to obtain first floor thin film on substrate Film or ST thin film)；
Step 3, repeat the process of step 2, can obtain bst thin film on substrate and ST thin film is alternatively formed (2n+1) layer film；
Step 4, the substrate of band (2n+1) layer film step 3 obtained are positioned in Muffle furnace, at 650～800 DEG C At a temperature of be incubated 1～3h, carry out crystallization and thermal treatment, cooling, i.e. can get sandwich structure multilamellar of the present invention Thin film.
Comparative example 1
Prepare 7 layers of Ba0.6Sr0.4TiO3(BST) thin film, specifically includes following steps:
Step 1, at a temperature of 70～80 DEG C, by Barium acetate: strontium acetate: butyl titanate: polyvinylpyrrolidone Barium strontium titanate (the Ba of the molar ratio 0.25mol/L of=0.6:0.4:1:0.6%xSr1-xTiO3, BST) and colloidal sol；
Step 2, at Pt/Ti/SiO2On the Pt of/Si substrate, spin coating above-mentioned BST colloidal sol, turns with the rotating speed of 3500r/min Dynamic substrate 8s, then the rotational speed substrate 35s with 5500r/min；The most first it is placed in baking oven and is dried at 110 DEG C 15min, after taking-up, is positioned in Muffle furnace, is warming up to 350 DEG C with the heating rate of 10 DEG C/min, at 350 DEG C At a temperature of be pyrolyzed 10min, be finally warming up to 600 DEG C with the heating rate of 10 DEG C/min, at a temperature of 600 DEG C protect Temperature 10min, carries out pre-crystallization and thermal treatment, cools to room temperature with the furnace, takes out, i.e. obtains first floor BST on substrate Thin film；
Step 3, repeat the process 6 times of step 2,7 layers of bst thin film can be obtained on substrate；
Step 4, the substrate of the 7 layers of bst thin film of band step 3 obtained are positioned in Muffle furnace, 650 DEG C of temperature Lower insulation 1h, carries out crystallization and thermal treatment, cooling, i.e. can get 7 layers of bst thin film.
Comparative example 2
Prepare 7 layers of SrTiO3(ST) thin film, specifically includes following steps:
Step 1, at a temperature of 70～80 DEG C, by strontium acetate: the molar ratio 0.17mol/L of butyl titanate=1:1 Strontium titanates (SrTiO3, ST) and colloidal sol；
Step 2, at Pt/Ti/SiO2On the Pt of/Si substrate, spin coating above-mentioned ST colloidal sol, turns with the rotating speed of 3500r/min Dynamic substrate 8s, then the rotational speed substrate 35s with 5500r/min；The most first it is placed in baking oven and is dried at 110 DEG C 15min, after taking-up, is positioned in Muffle furnace, is warming up to 350 DEG C with the heating rate of 10 DEG C/min, at 350 DEG C At a temperature of be pyrolyzed 10min, be finally warming up to 600 DEG C with the heating rate of 10 DEG C/min, at a temperature of 600 DEG C protect Temperature 10min, carries out pre-crystallization and thermal treatment, cools to room temperature with the furnace, takes out, i.e. obtains first floor ST on substrate Thin film；
Step 3, repeat the process 6 times of step 2,7 layers of ST thin film can be obtained on substrate；
Step 4, the substrate of the 7 layers of ST thin film of band step 3 obtained are positioned in Muffle furnace, 650 DEG C of temperature Lower insulation 1h, carries out crystallization and thermal treatment, cooling, i.e. can get 7 layers of ST thin film.
Embodiment 1
The preparation method of a kind of BST/ST/BST/ST/BST/ST/BST7 layer film, comprises the following steps:
Step 1, at a temperature of 70～80 DEG C, by Barium acetate: strontium acetate: butyl titanate: polyvinylpyrrolidine Barium strontium titanate (the Ba of the molar ratio 0.25mol/L of ketone=0.6:0.4:1:0.6%xSr1-xTiO3, BST) and molten Glue；At a temperature of 70～80 DEG C, by strontium acetate: the molar ratio 0.17mol/L's of butyl titanate=1:1 Strontium titanates (SrTiO3, ST) and colloidal sol；
Step 2, at Pt/Ti/SiO2Spin coating BST colloidal sol on the Pt of/Si substrate, with the rotational speed base of 3500r/min Sheet 8s, then the rotational speed substrate 35s with 5500r/min；The most first it is placed in baking oven and at 110 DEG C, is dried 15min, After taking-up, it is positioned in Muffle furnace, is warming up to 350 DEG C with the heating rate of 10 DEG C/min, at a temperature of 350 DEG C Pyrolysis 10min, is finally warming up to 600 DEG C with the heating rate of 10 DEG C/min, is incubated 10min at a temperature of 600 DEG C, Carry out pre-crystallization and thermal treatment, cool to room temperature with the furnace, take out, on substrate, i.e. obtain first floor bst thin film；
Step 3, use the step identical with step 2, preparation on the first floor bst thin film that step 2 obtains successively Obtain ST/BST/ST/BST/ST/BST layer film；
Step 4, step 3 is processed after the substrate that obtains be positioned in Muffle furnace, at a temperature of 650 DEG C, be incubated 1h, Carry out crystallization and thermal treatment, cooling, i.e. can get BST/ST/BST/ST/BST/ST/BST7 layer film.
Embodiment 2
The preparation method of ST/BST/ST/BST/ST/BST/ST7 layer film, and differing only in of embodiment 1: First preparing ST thin film on substrate, remaining step is same as in Example 1.
Embodiment 3
The preparation method of KMgBST/ST/KMgBST/ST/KMgBST/ST/KMgBST7 layer film, including Following steps:
Step 1, at a temperature of 70～80 DEG C, by Barium acetate: strontium acetate: butyl titanate: polyvinylpyrrolidine Barium strontium titanate (the Ba of the molar ratio 0.25mol/L of ketone=0.6:0.4:1:0.6%xSr1-xTiO3, BST) and molten Glue；Being added by potassium acetate in glacial acetic acid, magnetic agitation at a temperature of 70～80 DEG C, until dissolving, is subsequently adding second Acyl acetone, ethylene glycol monomethyl ether and ethylene glycol, stir 5 hours at a temperature of 70～80 DEG C, obtain 0.2mol/L Potassium acetate precursor liquid；Magnesium acetate is added in glacial acetic acid, magnetic agitation at a temperature of 70～80 DEG C until dissolve, It is subsequently adding acetylacetone,2,4-pentanedione, ethylene glycol monomethyl ether and ethylene glycol, stirs 5 hours at a temperature of 70～80 DEG C, obtain The magnesium acetate precursor liquid of 0.2mol/L；Then, it is 1% according to the mol ratio of potassium acetate, magnesium acetate and BST: BST colloidal sol, potassium acetate precursor liquid and magnesium acetate precursor liquid are mixed by the ratio of 1%:1, and preparation obtains potassium magnesium Codope barium strontium titanate (KMgBST) colloidal sol；At a temperature of 70～80 DEG C, by strontium acetate: butyl titanate=1: Strontium titanates (the SrTiO of the molar ratio 0.17mol/L of 13, ST) and colloidal sol；
Step 2, at Pt/Ti/SiO2Spin coating KMgBST colloidal sol on the Pt of/Si substrate, turns with the rotating speed of 3500r/min Dynamic substrate 8s, then the rotational speed substrate 35s with 5500r/min；The most first it is placed in baking oven and is dried at 110 DEG C 15min, after taking-up, is positioned in Muffle furnace, is warming up to 350 DEG C with the heating rate of 10 DEG C/min, at 350 DEG C At a temperature of be pyrolyzed 10min, be finally warming up to 600 DEG C with the heating rate of 10 DEG C/min, at a temperature of 600 DEG C protect Temperature 10min, carries out pre-crystallization and thermal treatment, cools to room temperature with the furnace, takes out, i.e. obtains the first floor on substrate KMgBST thin film；
Step 3, use the step identical with step 2, successively on the first floor KMgBST thin film that step 2 obtains Prepare ST/KMgBST/ST/KMgBST/ST/KMgBST layer film；
Step 4, step 3 is processed after the substrate that obtains be positioned in Muffle furnace, at a temperature of 650 DEG C, be incubated 1h, Carry out crystallization and thermal treatment, cooling, i.e. can get KMgBST/ST/KMgBST/ST/KMgBST/ ST/KMgBST7 layer film (is called for short K1Mg1).
Embodiment 4
The present embodiment is distinguished as with embodiment 3: in step 1, potassium acetate, magnesium acetate with the mol ratio of BST are 1%:2%:1, remaining step (being called for short K1Mg2) same as in Example 3.
Embodiment 5
The present embodiment is distinguished as with embodiment 3: in step 1, potassium acetate, magnesium acetate with the mol ratio of BST are 2%:2%:1, remaining step (being called for short K2Mg2) same as in Example 3.
Embodiment 6
The present embodiment is distinguished as with embodiment 3: in step 1, potassium acetate, magnesium acetate with the mol ratio of BST are 4%:1%:1, remaining step (being called for short K4Mg1) same as in Example 3.
Embodiment 7
The preparation method of ST/KMgBST/ST/KMgBST/ST/KMgBST/ST7 layer film, with embodiment 3 Be distinguished as: potassium acetate in step 1, magnesium acetate are 2%:2%:1 with the mol ratio of BST, in step 2 first Prepare ST thin film (being called for short K2Mg2*).
The XRD diffracting spectrum of the thin film that Fig. 3 is embodiment 1,2 and comparative example 1,2 obtains；From the figure 3, it may be seen that The thin film that embodiment 1,2 and comparative example 1,2 obtain is main to be grown along (110) crystal face, and highly crystallization, in typical case ABO3Perovskite structure；The thin film that embodiment 1,2 obtains, compared with comparative example, demonstrates higher crystallization, Average crystal grain is obviously reduced.The average crystal grain size of the thin film that comparative example 1,2 obtains be respectively 29.8nm, 48.7nm, the average crystal grain size of the thin film that embodiment 1,2 obtains is respectively 20.7nm and 20.5nm；Show Lattice mismatch that ST thin film contributes to improving between bst thin film and substrate in sandwich structure, improve thin film shape Looks, crystal grain thinning and reduction surface roughness.Following table is the thin film (110) of embodiment 1,2 and comparative example 1,2 Characteristic peak parameter value:
Fig. 4 is the XRD diffracting spectrum of the thin film that embodiment 3-7 obtains；As shown in Figure 4, embodiment 3-7 The thin film obtained still demonstrates typical ABO3Perovskite structure, crystallization is more thorough, shows potassium mg-doped energy Strengthen crystallization, make lattice paprmeter and average crystal grain reduce.Following table is thin film (110) the characteristic peak ginseng of embodiment 3-7 Numerical value:
Fig. 5 is the SEM figure of the thin film that comparative example 1 (a) obtains with embodiment 1 (b)；As shown in Figure 5, with right Ratio 1 is compared, and the thin film crystallite dimension that embodiment 1 obtains is obviously reduced, surface compact Du Genggao.Fig. 6 is real Execute example 5 and the SEM figure of thin film that embodiment 6 obtains；It will be appreciated from fig. 6 that the crystallite dimension of thin film is obviously reduced, Surface compact Du Genggao, shows that potassium mg-doped contributes to crystal grain thinning, reduces surface roughness, improves surface shape Looks.
(a) that the thin film that Fig. 7 is comparative example 1,2 and embodiment 1,2 obtains is tested under room temperature and 100kHz Electric capacity, (b) dielectric loss, (c) tuning rate curve；As shown in Figure 7, comparative example 1, comparative example 2, embodiment 1, the capacitance size of the thin film of embodiment 2 is respectively 139pF～424pF, 113pF～133pF, 163pF～351pF With 150pF～244pF, the dielectric loss of embodiment 1,2 thin film has compared with comparative example 1,2 and reduces significantly, Embodiment 1 thin film maintains the high tuning rate of 53.6% under the low bias of 10V.Sandwich structure multilamellar of the present invention Thin film can effectively combine the advantage of bst thin film and ST thin film, reduces loss while humorous rate of keeping a high profile.
Fig. 8 is the thin film that obtains of embodiment 3-6 tuning rate test curve under room temperature and 100kHz；By scheming 8 understand, and embodiment 3,4,5,6 thin film all reaches higher tuning rate, embodiment under the low bias of 10V 3, the tuning rate of 4 thin film has exceeded 45%, and the thin film tuning rate of embodiment 5,6, more than 50%, is respectively 52.3% and 51.7%.
Fig. 9 is the thin film that obtains of embodiment 3-6 dielectric loss test curve under room temperature and 100kHz；By Fig. 9 understands, and the thin film that embodiment 3-6 obtains is compared with comparative example 1, and dielectric loss significantly reduces.
Dielectric properties test under height biases shows, the resistance to breakdown strength of Sandwich film of the present invention is with right Ratio is compared and is remarkably reinforced, and the most breakdown in the range of-40V～40V, ± 40V tuning rate between 65～82%, dielectric loss is between 0.012～0.026.
Following table is the dielectric properties parameter of the thin film that embodiment 3-7 obtains:
Membrane structure Bias 0V electric capacity (pF) 0V is lost 10V damages Tuning rate FOM
K (1%) &Mg (1%) ±10V 288 0.021 0.014 45.7 32.6
K (1%) &Mg (2%) ±10V 197 0.024 0.017 46.3 27.2
K (2%) &Mg (2%) ±10V 108 0.014 0.008 52.3 65.4
K (4%) &Mg (1%) ±10V 166 0.022 0.011 51.7 47
K (2%) &Mg (2%) * ±10V 272 0.011 0.0074 51.4 69.5
Figure 10 is the thin film (i.e. K2Mg2*) that obtains of embodiment 7 tuning rate under room temperature and 100kHz and Jie Electrical loss test curve；As shown in Figure 10, embodiment 7 thin film has higher tuning rate and low Jie simultaneously Electrical loss.
To sum up, present invention thin film based on potassium magnesium codope BST tuning rate under low bias is more than 50%, dielectric Loss 0.004～0.006, FOM is more than 90, and dielectric strength is more than 40V, fully meets microwave-tuned application.
Sandwich film of the present invention is simultaneously achieved high tuning rate and the dielectric substantially reduced under low bias Loss, FOM substantially increases, and Sandwich film based on potassium magnesium codope BST layer damages because of dielectric The amplitude that consumption reduces is bigger and has higher FOM, shows more much higher than bst thin film under height biases Dielectric strength, significantly improve service life and practicality, for the comprehensive dielectric properties of bst thin film significantly Improve and provide effective way, provide in the actual application of the numerous areas including microwave-tuned device for it Strong material base and technical support.

Claims (11)

1. sandwich structure plural layers, (2n+1) layer film being alternatively formed including thin film A, thin film B；When described thin film A is KMgBST or bst thin film, described thin film B is ST thin film；When described thin film A is ST thin film, described thin film B is KMgBST or bst thin film；The thickness of described bst thin film, KMgBST thin film and ST thin film is 80～160nm.
Sandwich structure plural layers the most according to claim 1, it is characterized in that, described KMgBST is potassium and the barium strontium titanate of magnesium codope, the concrete preparation process of KMgBST thin film is: first, by soluble barium salt: solubility strontium salt: butyl titanate: polyvinylpyrrolidone=x:(1-x): the molar ratio BST colloidal sol of 1:y, soluble potassium salt precursor liquid and soluble magnesium salt precursor liquid is added in the BST colloidal sol obtained, preparation obtains KMgBST colloidal sol, wherein, soluble potassium salt, solubility magnesium salt are z with the mol ratio of BST1: z2: 1, x=0.2～0.8, y=0.5%～0.7%, z1、z2=1%～20%；Then spin coating above-mentioned KMgBST colloidal sol on substrate, drying, pyrolysis, after pre-crystallization and thermal treatment, cooling, on substrate, i.e. obtain KMgBST thin film.
3. a preparation method for sandwich structure plural layers, comprises the following steps:
Step 1, by soluble barium salt: solubility strontium salt: butyl titanate: polyvinylpyrrolidone=x:(1-x): the molar ratio BST colloidal sol of 1:y, soluble potassium salt precursor liquid and soluble magnesium salt precursor liquid is added in the BST colloidal sol obtained, preparation obtains KMgBST colloidal sol, wherein, soluble potassium salt, solubility magnesium salt are z with the mol ratio of BST1: z2: 1；By solubility strontium salt: the molar ratio ST colloidal sol of butyl titanate=1:1；Wherein, x=0.2～0.8, y=0.5%～0.7%, z1、z2=1%～20%；
Step 2, at Pt/Ti/SiO2Spin coating KMgBST colloidal sol or ST colloidal sol on/Si substrate, drying, pyrolysis, after pre-crystallization and thermal treatment, cooling, on substrate, i.e. obtain KMgBST thin film or ST thin film；
Step 3, repeat the process of step 2, KMgBST thin film can be obtained on substrate and (2n+1) layer film that ST thin film is alternatively formed；
Step 4, (2n+1) layer film step 3 obtained carry out crystallization and thermal treatment, cooling, i.e. can get sandwich structure plural layers of the present invention.
4. a preparation method for sandwich structure plural layers, comprises the following steps:
Step 1, by soluble barium salt: solubility strontium salt: butyl titanate: polyvinylpyrrolidone=x:(1-x): the molar ratio BST colloidal sol of 1:y；By solubility strontium salt: the molar ratio ST colloidal sol of butyl titanate=1:1；Wherein, x=0.2～0.8, y=0.5%～0.7%；
Step 2, at Pt/Ti/SiO2Spin coating BST colloidal sol or ST colloidal sol on/Si substrate, drying, pyrolysis, after pre-crystallization and thermal treatment, cooling, on substrate, i.e. obtain bst thin film or ST thin film；
Step 3, repeat the process of step 2, bst thin film can be obtained on substrate and (2n+1) layer film that ST thin film is alternatively formed；
Step 4, (2n+1) layer film step 3 obtained carry out crystallization and thermal treatment, cooling, i.e. can get sandwich structure plural layers of the present invention.
5., according to the preparation method of the sandwich structure plural layers described in claim 3 or 4, it is characterised in that soluble barium salt described in step 1 is Barium acetate, barium nitrate or barium chloride, solubility strontium salt is strontium acetate or strontium nitrate.
6. according to the preparation method of the sandwich structure plural layers described in claim 3 or 4, it is characterised in that the molar concentration of BST colloidal sol described in step 1 is 0.2～0.4mol/L；The molar concentration of ST colloidal sol is 0.15～0.2mol/L.
7., according to the preparation method of the sandwich structure plural layers described in claim 3 or 4, it is characterised in that described in step 4, crystallization and thermal treatment temperature is 650～800 DEG C, the time is 1～3h.
The preparation method of sandwich structure plural layers the most according to claim 3, it is characterised in that soluble potassium salt described in step 1 is potassium acetate, potassium chloride or potassium nitrate, described solubility magnesium salt is magnesium acetate, magnesium chloride or magnesium nitrate.
The preparation method of sandwich structure plural layers the most according to claim 3, it is characterised in that the molar concentration of described soluble potassium salt precursor liquid and soluble magnesium salt precursor liquid is 0.2～0.25mol/L.
The preparation method of sandwich structure plural layers the most according to claim 3, it is characterized in that, the concrete preparation process of KMgBST thin film described in step 2 or ST thin film is: first drop on substrate by KMgBST colloidal sol or ST colloidal sol, rotational speed substrate 6～8s with 3000～4000r/min, then the rotational speed substrate 30～40s with 3500～5500r/min；The most first it is placed in baking oven and at 100～120 DEG C, is dried 15～20min, in Muffle furnace, at a temperature of 300～400 DEG C, it is pyrolyzed 10～15min again, in Muffle furnace, finally at a temperature of 550～650 DEG C, is incubated 5～10min, carries out pre-crystallization and thermal treatment, cool to room temperature with the furnace, take out.
The preparation method of 11. sandwich structure plural layers according to claim 4, it is characterized in that, the concrete preparation process of bst thin film described in step 2 or ST thin film is: first drop on substrate by BST colloidal sol or ST colloidal sol, rotational speed substrate 6～8s with 3000～4000r/min, then the rotational speed substrate 30～40s with 3500～5500r/min；The most first it is placed in baking oven and at 100～120 DEG C, is dried 15～20min, in Muffle furnace, at a temperature of 300～400 DEG C, it is pyrolyzed 10～15min again, in Muffle furnace, finally at a temperature of 550～650 DEG C, is incubated 5～10min, carries out pre-crystallization and thermal treatment, cool to room temperature with the furnace, take out.
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CN109060890A (en) * 2018-06-19 2018-12-21 陕西科技大学 A kind of preparation method with sandwich structure sensitive film
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CN108623301A (en) * 2018-06-13 2018-10-09 陕西科技大学 A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure
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