CN101230272A - Etching solution for etching BST film and preparation method thereof - Google Patents
Etching solution for etching BST film and preparation method thereof Download PDFInfo
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- CN101230272A CN101230272A CNA2008100453218A CN200810045321A CN101230272A CN 101230272 A CN101230272 A CN 101230272A CN A2008100453218 A CNA2008100453218 A CN A2008100453218A CN 200810045321 A CN200810045321 A CN 200810045321A CN 101230272 A CN101230272 A CN 101230272A
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- bst
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- corrosive fluid
- thin film
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Abstract
The invention provides an etch solution for etching BST film and the preparation method, which relates to an etch solution which can etch BST film treated by high-temperature crystallization, and belongs to microelectronics technology field, in particular relates to visualization process in electronic film preparing technology. The constituent of the invention contains HNO3, by volume ratio calculation, the ratios of BHF to HNO3to H2O equal to a to x to b, among which the x is less than or equal to 3 and is more than or equal to 0.5, the a is less than or equal to 2 and is more than or equal to 1, the b is less than or equal to 6 and is more than or equal to 5. The invention has the advantage that the etch solution of the invention can completely etch the BST material with clear edges and sharp section.
Description
Technical field
But the present invention relates to a kind of corrosive fluid of bst thin film of etching high temperature crystallization processing, belong to microelectronics technology, particularly the graphical process in the electric thin technology of preparing.
Background technology
Telecommunication technology, Radar Technology be to higher frequency, bigger bandwidth and more the direction of high amount of traffic amount develop, promoted the development and the innovation of high-frequency element.Wherein, the tunable high-frequency device as the core component of communication of future generation and radar system more and more is subjected to people's attention with its superior performance.Strontium-barium titanate (BST) film is because of its high-k, the high-k tuning rate, property such as low-dielectric loss and high breakdown electric field can obtain and the suitable even higher tuning rate of traditional tuning circuit under littler voltage drives, has high switching speed simultaneously, low driving power, size is little in light weight, low cost and other advantages, be applied to retarding line more and more, phase shifter, wave filter, high frequency devices such as resonator.
At present, chemical vapour deposition (MOCVD), pulsed laser deposition (PLD), magnetron sputtering, sol-gel method technologies such as (Sol-Gel) are mainly adopted in the preparation of bst thin film.Wherein, magnetron sputtering is the proven technique of preparation ferroelectric membranc, and it is low that it has a underlayer temperature, and the thin film crystallization of preparation is good; Good with ic process compatibility; Advantages such as the ferroelectricity of film is good.
Bst thin film with method for preparing need be handled through crystallization, along with the grain-size of the raising bst thin film of crystallization temperature increases, its density improves with the raising of crystallization temperature, and the electricity and the optical property of bst thin film also improve along with the raising of crystallization temperature.It is crucial that crystallization temperature is that the raising to the bst thin film tuning rate plays a part.Experiment shows that the bst thin film of crystallization temperature between 800 ℃～1000 ℃ has best tuning rate.
Micrographicsization is one of bst thin film key technologies for application, and bst thin film micrographics method commonly used is an etching.The dry etching bst thin film has figure and transforms the high and fabulous characteristics such as anisotropy of precision, but the required equipment costliness, and etch rate is low, to bottom electrode Pt poor selectivity, and easily causes the charing of photoresist material mask and is difficult to removal.Wet etching is that a kind of cost is low, the bst thin film graphic method that etch rate is fast, and for the figure of characteristic dimension greater than 3 μ m, wet etching can yet be regarded as a kind of economy and practical bst thin film figure method for transformation.
Traditional BST wet etching liquid uses the mixing solutions of hydrofluoric acid and water, this corrosive fluid can only corrode the bst thin film that adopts Prepared by Sol Gel Method and crystallization temperature at the bst thin film of the preparation of the magnetron sputtering below 600 ℃, has greatly limited the application of bst thin film in the tunable high-frequency device.
Summary of the invention
Technical problem to be solved by this invention is, a kind of corrosive fluid and preparation method who is used for etching BST film is provided, and adopts corrosive fluid etching BST film of the present invention, the crystallization temperature height and the edge clear of bst thin film, and lateral erosion is than little.
The technical scheme that the present invention solve the technical problem employing is, is used for the corrosive fluid of etching BST film, contains HNO in its component
3, calculate BHF: HNO with volume ratio
3: H
2O=a: x: b, wherein 0.5≤x≤3,1≤a≤2,5≤b≤6.Its best proportioning is a=1, b=5, x=2.
The component of described BHF is calculated with volume ratio, HF: NH
3F: H
2O=d1: d2: d3, wherein 0.5≤d1≤1,1.5≤d2≤2.5,3≤d3≤4.
The present invention also provides a kind of preparation to be used for the method for the corrosive fluid of etching BST film, may further comprise the steps:
The first step dose volume is than the HF solution that is 50%, HF: H
2O=1: 1;
The second step dose volume ratio is 40% NH
3F solution, NH
3F: H
2O=2: 3;
The 3rd step preparation buffered hydrofluoric acid solution B HF, 50% HF: 40% NH
3F=1: 5;
The 4th step preparation HNO
3The volume ratio scope is 0.5～3 BST corrosive fluid, and component is
BHF: HNO
3: H
2O=1: x: 5 0.5≤x≤3 wherein.
The invention has the beneficial effects as follows that corrosive fluid of the present invention can corrode the BST material comparatively completely, and edge clear, the cross section is precipitous.
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is bst thin film EDS figure, wherein, and (a) before the corrosion; (b) after the corrosion of employing BHF corrosive fluid; (c) adopt BHF/HNO
3/ H
2After the corrosion of O corrosive fluid.
Fig. 2 is the bst thin film SEM image after the corrosive fluid corrosion of the present invention.Wherein, 1 is the lanthanum aluminate substrate among the figure, and 2 is barium strontium titanate.
Fig. 3 is the bst thin film section S EM image after the corrosive fluid corrosion of the present invention.Wherein, sign 1 is the lanthanum aluminate substrate among the figure, and 2 is barium strontium titanate.
Fig. 4 is BHF/HNO
3/ H
2O corrosive fluid HNO
3The graph of relation of volume ratio and erosion rate and crystallization temperature.
Embodiment
The invention provides a kind of corrosive fluid that is used for etching BST film, it is characterized in that, contain HNO in its component
3, calculate BHF: HNO with volume ratio
3: H
2O=a: x: b, wherein 0.5≤x≤3,1≤a≤2,5≤b≤6.
Wherein, the component of BHF is calculated with volume ratio, HF: NH
3F: H
2O=d1: d2: d3, wherein 0.5≤d1≤1,1.5≤d2≤2.5,3≤d3≤4.
As embodiment, it is as follows that above-mentioned numerical value can be distinguished value:
| x | a | b | d1 | d2 | d3 | |
| Embodiment 1 | 1 | 1 | 5 | 0.5 | 2 | 3.5 |
| |
1.5 | 1 | 5 | 1 | 2 | 3.5 |
| Embodiment 3 | 2 | 1 | 5 | 1 | 2.5 | 4 |
The present invention also provides a kind of preparation to be used for the method for the corrosive fluid of etching BST film, it is characterized in that, may further comprise the steps:
The first step dose volume is than the HF solution that is 50%, HF: H
2O=1: 1;
The second step dose volume ratio is 40% NH
3F solution, NH
3F: H
2O=2: 3;
The 3rd step preparation buffered hydrofluoric acid solution B HF, 50% HF: 40% NH
3F=1: 5;
The 4th step preparation HNO
3The volume ratio scope is 0.5～3 BST corrosive fluid, and component is
BHF: HNO
3: H
2O=1: x: 5 0.5≤x≤3 wherein.
As another embodiment, the present invention adopts rf magnetron sputtering to prepare bst thin film, sputtering pressure 0.1Pa, and gas flow rate is than Ar: O
2=1: 5, power density 1.85Wcm
-2, target Ba
0.6Sr
0.4TiO
3, target size φ 120mm, substrate temperature is 400 ℃ during sputter, substrate Pt/LaAlO
3(100).800 ℃～1000 ℃ of crystallization temperature scopes.The bst thin film preparatory phase, corrosive fluid bst thin film B component applicatory a
0.5Sr
0.5TiO
3, Ba
0.6Sr
0.4TiO
3, Ba
0.65Sr
0.35TiO
3BST adopts rf magnetron sputtering, and substrate is cooked the planetary orbit operation scheme that revolution adds rotation in sputter procedure, adopt this mode to improve the homogeneity of deposit film.Bst thin film sputters on lanthanum aluminate substrate (LAO) substrate.
Adopt corrosive fluid of the present invention that bst thin film is corroded, in sealed plastic container, 50 ℃ of heating in water bath adopt encloses container can prevent HNO in the heating corrosion process
3Volatilization.The solution preparation is at room temperature carried out.
As Fig. 1, before corrosion, each component of bst thin film all exists and does not have an impurity element, adopts behind the BHF corrosive fluid in the bst thin film, and the Ba element disappears, but Ti and Sr element do not corrode totally, adds HNO in BHF
3After, the BST all elements all corrodes totally.Fig. 2 is process BHF/HNO of the present invention
3/ H
2Bst thin film SEM image after the O corrosion, the etching edge clear, lateral erosion was than 0.5: 1.
Fig. 3 is BHF/HNO of the present invention
3/ H
2Bst thin film section S EM image after the O corrosion, the bst thin film cross section is precipitous after the visible etching.
Fig. 4 is corrosive fluid HNO
3The relation of volume ratio and erosion rate and crystallization temperature.As seen from the figure, erosion rate is with HNO
3The increase of volume ratio and increasing reduces with the raising of crystallization temperature.
Claims (4)
1. be used for the corrosive fluid of etching BST film, it is characterized in that, contain HNO in its component
3, calculate BHF: HNO with volume ratio
3: H
2O=a: x: b, wherein 0.5≤x≤3,1≤a≤2,5≤b≤6.
2. the corrosive fluid that is used for etching BST film as claimed in claim 1 is characterized in that, a=1, b=5, x=2.
3. the corrosive fluid that is used for etching BST film as claimed in claim 1 is characterized in that the component of described BHF is calculated with volume ratio, HF: NH
3F: H
2O=d1: d2: d3, wherein 0.5≤d1≤1,1.5≤d2≤2.5,3≤d3≤4.
4. a method for preparing the corrosive fluid that is used for etching BST film is characterized in that, may further comprise the steps:
The first step dose volume is than the HF solution that is 50%, HF: H
2O=1: 1;
The second step dose volume ratio is 40% NH
3F solution, NH
3F: H
2O=2: 3;
The 3rd step preparation buffered hydrofluoric acid solution B HF, 50% HF:40% NH
3F=1: 5;
The 4th step preparation HNO
3The volume ratio scope is 0.5～3 BST corrosive fluid, and component is BHF: HNO
3: H
2O=1: x: 5 0.5≤x≤3 wherein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100453218A CN101230272B (en) | 2008-01-31 | 2008-01-31 | Etching solution for etching BST film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100453218A CN101230272B (en) | 2008-01-31 | 2008-01-31 | Etching solution for etching BST film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101230272A true CN101230272A (en) | 2008-07-30 |
| CN101230272B CN101230272B (en) | 2011-04-27 |
Family
ID=39897098
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100453218A Expired - Fee Related CN101230272B (en) | 2008-01-31 | 2008-01-31 | Etching solution for etching BST film and preparation method thereof |
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| Country | Link |
|---|---|
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2008
- 2008-01-31 CN CN2008100453218A patent/CN101230272B/en not_active Expired - Fee Related
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|---|---|
| CN101230272B (en) | 2011-04-27 |
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Granted publication date: 20110427 Termination date: 20140131 |