CN101777424B - Photoetching preparation method of PVDF (Polyvinylidene Fluoride) organic polymer film capacitor - Google Patents
Photoetching preparation method of PVDF (Polyvinylidene Fluoride) organic polymer film capacitor Download PDFInfo
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Abstract
The invention discloses a photoetching preparation method of a PVDF (Polyvinylidene Fluoride) organic polymer film capacitor. The method is characterized by comprising the following steps of: depositing a metal bottom electrode at low temperature on a substrate by using a thermal evaporation apparatus, then sputtering and growing a silicon dioxide or silicon nitride dielectric insulating layer on the bottom electrode; carrying out photoetching corrosion on the silicon dioxide or silicon nitride dielectric insulating layer to form an opening of a functional area of a PVDF organic polymer film; preparing the PVDF organic polymer film; depositing a metal top electrode at low temperature on the PVDF organic polymer film; carrying out the photoetching corrosion on the metal top electrode; etching by using oxygen plasma to remove the PVDF organic polymer film of a nonfunctional area and the remaining photoresist; thermally evaporating and depositing a wrapping electrode at low temperature on the metal top electrode; carrying out the photoetching corrosion to remove the excessive wrapping electrode; and finishing the preparation of the PVDF organic polymer film capacitor. The photoetching preparation method improves the stability and reliability of the device, and makes it possible to prepare and integrate a small panel, range of lines and area array device.
Description
Technical field
The present invention relates to the electronic devices and components manufacturing technology, specifically refer to a kind of optical graving Preparation Method of PVDF organic polymer thin film capacitor.
Background technology
In recent years, organic polymer thin film is because electrology characteristic is good, technology is simple, cost is low, be subjected to extensive concern with excellent specific property such as various organic and inorganic substrate compatibilities, moved towards the preparatory phase of various organic assemblies from investigation of materials, its photoelectric respone can compare favourably with inorganic material, simultaneously, in fields such as demonstration, radio frequency identification system, smart cards for storage huge potential application is arranged, promoted the generation of active circuit on organic substrate.
The preparation method of organic polymer thin film is different from inorganic thin film fully.At present, two kinds of technologies are mainly adopted in the preparation of organic polymer thin film: one, and technologies such as sol-gal process or LB film are carried out chemistry or heat treatment to organic film then, represent material to be present emerging PVDF film; Two, vacuum molecule bundle sedimentation, heat deposition organic film in vacuum chamber, representing material is the pentacene organic semiconductor thin-film of present excellent performance.No matter be the organic film of the sort of method preparation, photoetching all is the difficult problem in the present organic assembly preparation.Because the chemical reagent that conventional photoetching process is used is organic solvent, organic polymer thin film and its generation chemical reaction, so organic film can't adopt conventional photoetching process.
With traditional PVDF organic polymer capacitor arrangement is example, have only hearth electrode can adopt common process to carry out the photoetching preparation in the device preparation, after adopting sol-gal process or LB embrane method to prepare organic film, since can't photoetching, top electrode can only adopt metal mask plate growth or spraying printing technology.The outstanding problem of this capacitor arrangement is: one, because can't photoetching, functional areas can not accurately be determined, outside the side, functional areas is exposed to, have influenced the stability and the reliability of device; Two, self isolates upper/lower electrode as dielectric layer organic polymer thin film, has point effect in edge, easily punctures; Three, nonfunctional area can't influence the measurement of adjacent devices by method selective removals such as etchings, and the easy cascade of device is punctured, seriously restricted simultaneously bottom electrode drawing and with the interconnection of other components and parts; Four, because the accuracy limitations of metal mask plate or printing spraying technology, the area minimum of top electrode can only arrive 200 μ m * 200 μ m, this has greatly limited the precision and the yardstick of technology, can't carry out accurate facet components and parts and alignment, face battle array preparation of devices, limit the range of application of organic assembly; Five, because PVDF organic film and photoetching solvent react, this makes capacitor devices can't proceed traditional handicraft as the backend steps of device technology, has limited integrated with other devices.
Summary of the invention
The objective of the invention is to overcome the difficult problem that PVDF thin polymer film in the existing PVDF capacitor devices technology can't photoetching, a kind of photoetching technology of preparing of PVDF organic polymer thin film capacitor is proposed, this PVDF organic polymer capacitor arrangement can solve the edge breakdown effect of capacitor, and melt convenient and other devices integrated mutually with the subsequent optical carving technology.
The capacitor devices of a kind of PVDF organic polymer thin film of the present invention photoetching method preparation is characterized in that device architecture comprises:
One substrate;
One metallic bottom electrode, this metallic bottom electrode is grown on the substrate;
One dielectric insulation layer, this dielectric insulation layer is grown on the metallic bottom electrode, and the edge falls within on the substrate, and perforate is arranged;
One organic polymer thin film, this organic polymer thin film is grown in the dielectric insulation layer perforate, and the area of this organic polymer thin film is greater than the perforated area of dielectric insulation layer, and the edge drops on the dielectric insulation layer;
One electrode of metal, this electrode of metal are grown on the organic polymer thin film layer, and its area is identical with organic polymer thin film functional areas area;
One parcel electrode, this parcel electrode wraps up organic polymer thin film side and electrode of metal, and the edge drops on the dielectric insulation layer.
Wherein substrate is sapphire, silicon, gallium nitride or ito glass.
Wherein metallic bottom electrode is the aluminium electrode of thermal evaporation low temperature depositing, and thickness is not less than 100nm, and electrode is a rectangle structure.
Wherein dielectric insulation layer is silicon dioxide or silicon nitride dielectric layer, and the dielectric insulation layer edge is positioned on the substrate, is pass, and dielectric insulation layer wraps up the part metals hearth electrode, and perforate is slightly less than the functional areas area of device, and thickness is not less than 300nm.
Wherein organic polymer thin film is the PVDF film of sol-gal process or the preparation of LB embrane method, and thickness is 30nm-300nm.
Wherein electrode of metal is the aluminium electrode of thermal evaporation low temperature depositing, and thickness is not less than 100nm, and this electrode of metal area is identical with PVDF organic polymer thin film functional areas area.
The thickness that wherein wraps up electrode and be the thermal evaporation deposition is not less than the gold electrode of 150nm, electrode is a rectangle structure, be crossed as cross with bottom electrode, the edge drops on the dielectric insulation layer, its area wraps up side, PVDF organic polymer thin film functional areas and electrode of metal greater than PVDF organic polymer thin film functional areas area.
The optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor of the present invention device is characterized in that processing step is as follows:
1 utilizes thermal evaporation apparatus low temperature depositing metallic bottom electrode on substrate;
2 on hearth electrode sputter growthing silica or silicon nitride dielectric insulation layer;
3 photoetching corrosion silicon dioxide or silicon nitride dielectric insulation layer, the electrode of formation PVDF organic polymer thin film;
4 sol-gal processes or LB embrane method prepare the PVDF organic polymer thin film;
5 utilize thermal evaporation apparatus low temperature depositing electrode of metal on the PVDF organic polymer thin film;
6 photoetching corrosion electrode of metal;
7 oxygen plasma etches are removed nonfunctional area PVDF organic polymer thin film and residual photoresist;
8 on electrode of metal thermal evaporation low temperature depositing parcel electrode;
9 photoetching corrosions are removed unnecessary parcel electrode, finish PVDF organic polymer thin film capacitor preparation of devices.
Wherein said substrate is sapphire, silicon, gallium nitride or ito glass.
Wherein metallic bottom electrode is the aluminium electrode of thermal evaporation low temperature depositing, and thickness is not less than 100nm, and electrode is a rectangle structure.
Wherein the dielectric insulation layer corrosive liquid is selected the HF buffer solution for use.
Wherein organic polymer thin film is the PVDF film of sol-gal process or the preparation of LB embrane method, and thickness is 30nm-300nm.
Wherein the electrode of metal of thermal evaporation low temperature depositing is the Al film that thickness is not less than 100nm on the organic polymer thin film, and corrosive liquid is selected phosphoric acid for use.
The thickness that wherein wraps up electrode and be the thermal evaporation low temperature depositing is not less than the gold electrode of 150nm, electrode is a rectangle structure, be crossed as cross with bottom electrode, the edge drops on the dielectric insulation layer, its area wraps up PVDF organic polymer thin film side and electrode of metal greater than the electrode of metal area.
Wherein unnecessary parcel electrode adopts etching process to remove, and corrosive liquid is 1: 4: 10 iodine of mass ratio, iodate ammonia, the aqueous solution.
The photoetching preparation technology of PVDF organic polymer thin film capacitor device of the present invention, it is characterized in that: the dielectric insulation layer of on metallic bottom electrode, growing earlier, isolated upper/lower electrode, and determine PVDF device function district area, the problem of having avoided traditional devices marginal existence point effect easily to puncture by the corrosion perforate; Utilize capacitor top electrode as PVDF thin film photolithography mask, top electrode is adopted etching process, determine top electrode and PVDF functional areas figure simultaneously, overcome the technical barrier that the PVDF organic polymer thin film is soluble in conventional lithography solution, accurately controlled capacitor area; The oxygen plasma etching is removed photoresist and removed unnecessary nonfunctional area PVDF film when being removed residual photoresist, avoided crosstalking between the different units, made things convenient for bottom electrode draw and with the interconnection of other devices, thereby can realize alignment and face battle array preparation of devices and application; The parcel electrode wraps up side, PVDF organic polymer thin film functional areas and top electrode, avoided the exposure of sides, organic film functional areas, the reliability and stability of device have not only been guaranteed, and can carry out follow-up traditional handicraft thereon safely, as photoetching, burn into plated film etc., be the integrated technology basis of having accomplished fluently of organic polymer device and other kinds device, the PVDF device that is through with can only be as the history of conventional lithography process backend steps.
Description of drawings
Fig. 1 is the structural representation of PVDF organic polymer thin film capacitor device of the present invention, and wherein Fig. 1 (a) is the sectional view of PVDF organic polymer thin film capacitor device, and Fig. 1 (b) is the vertical view of PVDF organic polymer thin film capacitor device.
Fig. 2 is the process chart of PVDF organic polymer thin film capacitor device of the present invention.
Wherein: 1---substrate;
2---metallic bottom electrode;
3---dielectric insulation layer;
4---the PVDF organic polymer thin film;
5---electrode of metal;
6---residual photoresist;
7---the parcel electrode.
Embodiment
See also accompanying drawing 1, PVDF organic polymer thin film capacitor device of the present invention, its device architecture comprises:
One substrate 1, this substrate 1 is sapphire, silicon, gallium nitride or ito glass;
One capacitor bottom electrode 2, this hearth electrode 2 is a square-shaped electrode, is produced on the substrate 1, is not less than the Al film of 100nm for the thickness of prepared by heat evaporation;
One dielectric insulation layer 3, this dielectric insulation layer 3 is an open cell type, is grown on hearth electrode 2 and the part substrate 1, and the part hearth electrode is covered fully, and this dielectric insulation layer 3 is silicon dioxide or silicon nitride dielectric film, and thickness is not less than 300nm;
One organic polymer thin film 4, this organic polymer thin film is grown in the dielectric insulation layer perforate, area is greater than the perforated area of dielectric insulation layer, and the edge drops on the dielectric insulation layer, this organic polymer thin film is the PVDF film of sol-gal process or the preparation of LB embrane method, and thickness is 30nm-300nm;
One capacitor top electrode 5, these top electrode 5 preparations are on PVDF organic polymer thin film layer 4, and its area is identical with PVDF organic polymer thin film functional areas area, for being not less than the thick Al metallic film of 100nm.
One parcel electrode 6, this parcel electrode wraps up organic polymer thin film side and electrode of metal, and the edge drops on the dielectric insulation layer, and this parcel electrode is the gold electrode that the thickness of thermal evaporation deposition is not less than 150nm, electrode is a rectangle structure, is crossed as cross with bottom electrode.
Please consult Fig. 2 again, and in conjunction with Fig. 1, the photoetching preparation technology of PVDF organic polymer thin film capacitor device of the present invention, the device preparation may further comprise the steps:
1 utilizes thermal evaporation apparatus low temperature depositing metallic bottom electrode 2 on substrate 1, this substrate 1 is sapphire, silicon, gallium nitride or ito glass, and this capacitor bottom electrode 2 is the aluminium electrode of thermal evaporation low temperature depositing, and thickness is not less than 100nm, and electrode is a rectangle structure;
2 on capacitor bottom electrode 2 sputter growth dielectric insulation layer 3, and dielectric insulation layer 3 is carried out perforate by lithography corrosion process, this dielectric insulation layer 3 is grown on the metallic bottom electrode 2, the edge falls within on the substrate 1, for thickness is not less than silicon dioxide or the silicon nitride film of 300nm, wherein the dielectric insulation layer corrosive liquid is selected the HF buffer solution for use;
3 prepare organic polymer thin film 4 on dielectric insulation layer 3, this organic polymer thin film 4 is for utilizing the PVDF film of sol-gal process or LB embrane method preparation, and thickness is 30nm-300nm;
4 utilize thermal evaporation apparatus low temperature depositing electrode of metal 5 on organic polymer thin film 4, this electrode of metal 5 is not less than the Al metallic film of 100nm for thickness;
5 carry out conventional lithography on electrode of metal 5, and electrode of metal 5 is carried out wet etching, and corrosive liquid is selected phosphoric acid for use;
6 utilize oxygen plasma etch to remove simultaneously the nonfunctional area PVDF organic polymer thin film and residual photoresist 6;
7 on electrode of metal 5 thermal evaporation low temperature depositing parcel electrode 7, and by the unnecessary parcel electrode of conventional lithography erosion removal, the thickness that this parcel electrode is the thermal evaporation low temperature depositing is not less than the gold thin film of 150nm, electrode is a rectangle structure, be crossed as cross with bottom electrode, the edge drops on the dielectric insulation layer, its area is greater than the electrode of metal area, PVDF organic polymer thin film side and electrode of metal are wrapped up, wherein unnecessary parcel electrode adopts etching process to remove, and corrosive liquid is 1: 4: 10 iodine of mass ratio, iodate ammonia and the aqueous solution.
See also Fig. 1, the optical graving Preparation Method of PVDF organic polymer thin film capacitor device of the present invention, concrete preparation process is as follows: selecting sapphire for use is that substrate 1 utilizes method such as photoetching plated film to prepare capacitor bottom electrode 2 (Al electrode, thickness are 120nm, and area is 500 μ m * 800 μ m); Utilize sputtering method growth dielectric insulation layer 3 (SiO
2, thickness is 300nm, area is 500 μ m * 800 μ m), be crossed as cross with hearth electrode, and photoetching, hydrofluoric acid corrosion perforate (200 μ m * 200 μ m); Utilize Prepared by Sol Gel Method PVDF organic polymer thin film 4 (two-layer, thickness is about 120nm, 130 ℃ of annealing 3hour heat treatment); Thermal evaporation low temperature depositing capacitor top electrode 5 (Al electrodes on PVDF organic polymer thin film 4, thickness is 100nm), and by photoetching, wet etching (phosphoric acid, 45s) remove nonfunctional area Al metal electrode, utilize oxygen plasma etch nonfunctional area PVDF subsequently, remove residual photoresist 6 simultaneously, determine device PVDF functional areas area (300 μ m * 300 μ m); Utilize thermal evaporation low temperature depositing parcel electrode 7 at last, and utilize conventional lithography, corrosion to determine parcel electrode 7 figures (Au metallic film, thickness are 300nm, and area is 400 μ m * 800 μ m).
The PVDF organic polymer thin film capacitor structure that the present invention proposes is different from traditional organic polymer capacitor devices structure, it at first utilizes conventional lithography process growth capacitor bottom electrode on substrate, and preparing square type dielectric insulation layer with holes on the hearth electrode and on the part substrate, perforate is positioned on the metallic bottom electrode, and determined device area, isolated upper/lower electrode simultaneously, the problem of having avoided the traditional capacitor device edge easily to puncture; The organic polymer thin film of growing subsequently, utilize the organic polymer thin film capacitor top electrode PVDF thin polymer film to be carried out photoetching, etching as metal mask, PVDF polymer thin film pattern is identical with the top electrode area, the edge falls within on the dielectric insulation layer, so both avoided the easy problem of short-circuit of upper/lower electrode, make top electrode that the PVDF thin polymer film is played the mask effect again, avoided the exposure of function film, reduced the parasitic capacitance and the noise of device; The use of wrapping up electrode had simultaneously both made things convenient for the welding of device, again PVDF organic polymer thin film side and capacitor top electrode are wrapped up, follow-up traditional handicraft such as photoetching, burn into plated film etc. can be carried out on PVDF organic polymer thin film capacitor device safely, be the integrated technology basis of having accomplished fluently of organic polymer device and other kinds device.
Claims (11)
1. the optical graving Preparation Method of a PVDF organic polymer thin film capacitor device is characterized in that, the device preparation may further comprise the steps:
(1) on substrate, utilizes thermal evaporation apparatus low temperature depositing metallic bottom electrode;
(2) sputter growthing silica or silicon nitride dielectric insulation layer on hearth electrode;
(3) photoetching corrosion silicon dioxide or silicon nitride dielectric insulation layer form the functional areas perforate of PVDF organic polymer thin film;
(4) sol-gal process or LB embrane method prepare the PVDF organic polymer thin film;
(5) on the PVDF organic polymer thin film, utilize thermal evaporation apparatus low temperature depositing electrode of metal;
(6) photoetching corrosion electrode of metal;
(7) oxygen plasma etch is removed nonfunctional area PVDF organic polymer thin film and residual photoresist;
(8) thermal evaporation low temperature depositing parcel electrode on electrode of metal;
(9) photoetching corrosion is removed unnecessary parcel electrode, finishes PVDF organic polymer thin film capacitor preparation of devices.
2. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1 is characterized in that, wherein said substrate is sapphire, silicon, gallium nitride or ito glass.
3. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1 is characterized in that, wherein said metallic bottom electrode is the aluminium electrode of thermal evaporation low temperature depositing, and electrode is a rectangle structure, and thickness is not less than 100nm.
4. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1, it is characterized in that, wherein said dielectric insulation layer is magnetron sputtering growthing silica or silicon nitride dielectric layer, the dielectric insulation layer edge is positioned on the substrate, dielectric insulation layer is a pass, dielectric insulation layer wraps up the part metals hearth electrode, and perforate is slightly less than the functional areas area of device, and thickness is not less than 300nm.
5. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1 is characterized in that, wherein said dielectric insulation layer adopts hydrofluoric acid corrosion perforate.
6. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1 is characterized in that, wherein said organic polymer thin film is the PVDF film of sol-gal process or the preparation of LB embrane method, and thickness is 30nm-300nm.
7. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1, it is characterized in that, wherein said electrode of metal is the aluminium electrode of thermal evaporation low temperature depositing, and this electrode of metal area is identical with PVDF organic polymer thin film functional areas area.
8. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1 is characterized in that, the phosphoric acid corrosion corrosion is adopted in the unnecessary zone of wherein said electrode of metal.
9. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1 is characterized in that, wherein said nonfunctional area PVDF organic polymer thin film and residual photoresist adopt oxygen plasma etch to remove simultaneously.
10. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1, it is characterized in that, the thickness that wherein said parcel electrode is the thermal evaporation low temperature depositing is not less than the gold electrode of 150nm, electrode is a rectangle structure, be crossed as cross with bottom electrode, the edge drops on the dielectric insulation layer, and its area wraps up PVDF organic polymer thin film side and capacitor top electrode greater than the electrode of metal area.
11. the optical graving Preparation Method of a kind of PVDF organic polymer thin film capacitor device according to claim 1, it is characterized in that, wherein said unnecessary parcel electrode adopts etching process to remove, and corrosive liquid is 1: 4: 10 iodine of mass ratio, iodate ammonia and the aqueous solution.
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| CN2010101018786A CN101777424B (en) | 2010-01-27 | 2010-01-27 | Photoetching preparation method of PVDF (Polyvinylidene Fluoride) organic polymer film capacitor |
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| CN2010101018786A CN101777424B (en) | 2010-01-27 | 2010-01-27 | Photoetching preparation method of PVDF (Polyvinylidene Fluoride) organic polymer film capacitor |
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| US9793106B2 (en) | 2014-11-06 | 2017-10-17 | Texas Instruments Incorporated | Reliability improvement of polymer-based capacitors by moisture barrier |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044528C (en) * | 1996-09-05 | 1999-08-04 | 马开荣 | Thin-film thermosensitive resistance infrared detector |
| US6136643A (en) * | 1999-02-11 | 2000-10-24 | Vanguard International Semiconductor Company | Method for fabricating capacitor-over-bit-line dynamic random access memory (DRAM) using self-aligned contact etching technology |
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- 2010-01-27 CN CN2010101018786A patent/CN101777424B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044528C (en) * | 1996-09-05 | 1999-08-04 | 马开荣 | Thin-film thermosensitive resistance infrared detector |
| US6136643A (en) * | 1999-02-11 | 2000-10-24 | Vanguard International Semiconductor Company | Method for fabricating capacitor-over-bit-line dynamic random access memory (DRAM) using self-aligned contact etching technology |
Non-Patent Citations (2)
| Title |
|---|
| Jeong Hwan KIM，etc.Fabrication and Electrical Characteristics of Metal–Ferroelectric–Semiconductor Field Effect Transistor Based on Poly(vinylidene fluoride).《Japanese Journal of Applied Physics》.2008,第47卷(第11期),8472-8475. * |
| 韦波.基于CMOS制造工艺的电容型湿度传感器.《仪表技术与传感器》.2009,(第10期),16-17. * |
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