CN100422243C - Method of preparing ultra low dielectric constant polyimide membrane by polyamide ester precursor phase transformation - Google Patents
Method of preparing ultra low dielectric constant polyimide membrane by polyamide ester precursor phase transformation Download PDFInfo
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- CN100422243C CN100422243C CNB2006100532719A CN200610053271A CN100422243C CN 100422243 C CN100422243 C CN 100422243C CN B2006100532719 A CNB2006100532719 A CN B2006100532719A CN 200610053271 A CN200610053271 A CN 200610053271A CN 100422243 C CN100422243 C CN 100422243C
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Abstract
The invention discloses a preparing method of ultra-low dielectric constant polyimide film, which comprises the following steps: dissolving polyesteramide in the N, N-dimethyl acetamide, N, N-dimethyl formamide or N-methyl pyrrolidone to obtain the filming liquid with density at 15-30%; filtering the filming liquid; degassing; scraping on the stainless steel support to form liquid film with thickness at 50-500 um; solidifying support with liquid film in the hardening bath; immersing film to clean through alcohol or acetone; drying to obtain former film of polyesteramide; disposing the former film of polyesteramide in the nitrogen or argon gas to heat to obtain the product.
Description
Technical field
The technical field that the present invention relates to is the technology of preparing of polymer dielectric material for electrical, relates in particular to a kind of method of preparing ultra low dielectric constant polyimide membrane by polyamide ester precursor phase transformation.
Background technology
In recent years along with the continuous development of electronics, microelectronics industry, the integrated level of electronic and electrical equipment and element thereof improves constantly, device density and line density increase, live width reduces, cause the interfering noise of signal between resistance condenser coupled increase, signal or energy transmission delay, line losses and different circuit or energy to increase, directly influence the performance of equipment and element.In order to shorten the cycling time of signal and energy between conductor line, reduce cross interference and condenser coupling between transmission lag, circuit, satisfy the high speed that signal transmits, the function of raising equipment and element requires further to reduce the specific inductivity of interlayer dielectric material.
The specific inductivity of polymer materials usually between 3-8, high comprehensive performance, specific inductivity less than 3 or even the exploitation of the polymer materials of lower (as less than 2) be the main direction of dielectric materials development.Polyimide is that a class has good heat-resistant, electrical property and mechanical property, is widely used in the insulating material of microelectronics industry.Most polyimide generally are that precursor adopts the two-step approach preparation with the polyamic acid, at first in polar solvent, make the polyamic acid precursor solution of solubility, and then polyamic acid is obtained insoluble infusible polyimide by heating or chemically treated method cyclodehydration by tetracarboxylic dianhydride and diamine reactant.But, the polyamic acid instability, very sensitive to steam, in storage process, to degrade easily, molecular weight also usually changes in the hot-imide process; When the interlayer dielectric material, the carboxyl in the polyamic acid can with the metallic copper effect, make cupric ion be diffused into dielectric layer inside, reduce the insulating property of material; Polyamic acid is strong polar polymer, exists the intensive intermolecular hydrogen bonding between carboxyl, can only be dissolved in the strong polar aprotic solvent.Polyesteramide is the another kind of solubility precursor of polyimide, compare with polyamic acid, polyesteramide is a kind of metastable polymkeric substance, insensitive to steam, can there be degradation problem with the form long storage of solid-state or solution, the main chain DeR does not take place in the hot-imide process yet, and the solubility property of polyesteramide is better than polyamic acid, dissolves in many low boiling point organic solvents commonly used such as chloroform, methylene dichloride, tetrahydrofuran (THF), and can obtain high strong solution.Therefore, the method that replaces polyamic acid to prepare polyimide by polyesteramide more and more is subjected to investigator's attention.
The specific inductivity of polyimide can not satisfy the requirement of low-k in the microelectronic device technical development between 3-4, therefore the research of polyimide with ultra-low dielectric constant material in recent years causes people's attention gradually.The method of disclosed reduction polymide dielectric constant has:
(1) free volume of raising polyimide material: common method is to introduce some asymmetrical big monomers (as asymmetrical phenyl ring) in the polyimide segment, or some big side groups are introduced (in order to reduce electronic polarizability in irregularity ground on the polyimide segment, these side groups generally also all are fluoro-containing groups), destroy the symmetry of polymer molecular chain, make the distance between the molecular chain become big, thereby improve the free volume in the polyimide material.The asymmetric dianhydride and the diamines large volume monomer of employings such as Simpson band phenyl ring synthesize a series of polyimide (Thin Solid Films, 1997,308,480), fractional free volume rises to 1.34% by 0.58%, and specific inductivity drops to 2.73 by 3.07.But, the synthetic difficulty of the big monomer of asymmetry, raw material costliness; Because the free volume increase rate is limited, the polymide dielectric constant is difficult to be reduced to below 2.5.
(2) polarized action of group in the reduction polyimide molecule, the most frequently used means are to introduce fluorine atom or close fluorin radical in the polyimide molecule chain, reduce the polarization of molecule in electric field, thereby reduce the specific inductivity of polyimide, such as being that monomer has synthesized the fluorinated polyimide film with fluorine-containing dianhydride and fluorinated diamine among the patent US5401878, its specific inductivity is between 2.6-2.8; Obtained the polyimide of specific inductivity about 2.4 with hexafluorodianhydride with different diamine reactant among the EP0594947; Synthesized a kind of AB block copolymer (wherein, A is fluorine-containing unit, and B is the imide unit) among the JP2001220442, specific inductivity increases along with A unit weight percentage composition in the multipolymer and descends, and minimum is about 2.3.In the aforesaid method, introduce the chemosynthesis process complexity that fluoro-containing group reduces the polymide dielectric constant, implement the comparison difficulty, the leeway of material choice is little, cost is high, is unwell to scale production and use.In addition, the specific inductivity that obtains polyimide can not reach below 2.0, and the introducing of fluorine also will reduce heat-resisting, the solvent resistance and the mechanical property of polyimide material.
(3) the introducing air hole prepares polyimide porous (or foam) material.According to the dielectric principle, the specific inductivity of porous material depends on the specific inductivity of porosity and dense substrate.The specific inductivity of air is about 1.0, it is the minimum material of occurring in nature specific inductivity, the air that specific inductivity is minimum is introduced and is prepared into inner porous polyimide (the Thin Solid Films that is in the polyimide matrix, 2005,473,191), be to reduce the effective means of polymide dielectric constant, also be present unique specific inductivity that can make polyimide is reduced to the method below 2.0.
The preparation method of existing low dielectric coefficient polyimide porous film material mainly comprises: the unstable segment method of (1) thermolysis: adopt copolymerization or grafted method to make thermally labile segment and polyimide form multipolymer, by heating the thermally labile segment is decomposed, in polyimide matrix, stay hole and form hole, pertinent literature and patent have: (Polymer, 1995,36,4855), (Polymer International, 2004,53,1040), (Reactive and Functional Polymers, 1996,30,43), US5776990.(2) id reaction produces abscess method (JP2006022260): the small-molecule substance that produces by polyimide precursor generation imidization reaction is (as H
2O or ROH) foaming formation hole.(3) template hole forming method: adopt sol-gel method to prepare polyimide/nano silicon laminated film, laminated film is soaked in etching liquid, through washing and dry, obtain polyimide nano hole film, patent CN1760241 and CN200410083960.5 disclose this method.(4) supercritical carbon dioxide process: in polyimide precursor solution, add polymeric dispersant, make the polyimide precursor film; This film is immersed in extracts polymeric dispersant in the supercritical co,, obtain polyimide porous membrane (US6372808) through decompression, hot-imide; Perhaps, promptly obtain polyimide porous membrane (Advanced Materials, 2002,14,1041) behind the cooling decompression with soluble polyimide film swelling under the High Temperature High Pressure in supercritical co.All there are some problems separately in aforesaid method, and as feedstock production cost height, the shape of airport, size, porosity regulation and control are difficulty relatively; The specific inductivity of the soluble polyimide porous-film of supercritical carbon dioxide process preparation can reduce to 1.77, but soluble polyimide synthetic method complexity, costs an arm and a leg, and is unsuitable for mass-producing and uses.
In order further to reduce the specific inductivity of polyimide material, the contriver proposes a kind of method that adopts solubility precursor polyesteramide and solution inversion of phases principle to prepare ultra low dielectric constant polyimide membrane.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparing ultra low dielectric constant polyimide membrane by polyamide ester precursor phase transformation solves the problem that has low dielectric coefficient polyimide membrane preparation method complexity, cost height now, is difficult for mass-producing.
Method provided by the invention is that polyesteramide is dissolved in polar organic solvent N,N-dimethylacetamide, N, obtains the preparation liquid that mass concentration is 15-30% in dinethylformamide or the N-Methyl pyrrolidone; With preparation liquid after filtration, degassing back spreads to the liquid film that thickness is the 50-500 micron on the stainless steel supporter; The supporter that will have liquid film immerses in the precipitation bath and solidifies; Film after solidifying with ethanol or acetone soaking and washing, is obtained the polyamide ester precursor film after the drying; The polyamide ester precursor film is obtained ultra low dielectric constant polyimide membrane through gradient increased temperature imidization processing in nitrogen or argon gas.Described precipitation bath is water, ethanol or water and alcoholic acid mixed solution, and perhaps water and alcoholic acid mixed solution account for the mixed solution that 50-90%, above-mentioned solvent account for 10-50%.Described gradient increased temperature imidization treatment temp and time are: 150 ℃ following 1 hour, 220 ℃ following 1 hours, 350 ℃ are following 2 hours.
The molecular structural formula of described polyesteramide is:
Wherein, Ar
1For:
Ar
2For:
R is :-CH
3,-CH
2CH
3,-(CH
2)
2CH
3,-(CH
2)
3CH
3,-C (CH
3)
3
In order to make polyimide film surface compact, smooth, can before imidization, carry out surface densification, planarizing process: the dilute solution that polyesteramide and solvent is mixed with 2-6% to the polyamide ester precursor film, precursor film is soaked 20-40 second therein, take out after drying, and then imidization.Identical in described polyesteramide and solvent and the described preparation liquid.
The surface densification of polyimide film, leveling, also can directly realize: the dilute solution that polyesteramide and solvent is mixed with 2-6% from polyimide film, shaggy polyimide film is soaked 40-60 second therein, take out after drying and obtain the surperficial polyimide film of fine and close smooth polyesteramide layer that is, and then get final product through gradient increased temperature imidization processing.Identical in described polyesteramide and solvent and the described preparation liquid.
The invention has the beneficial effects as follows:
(1) the present invention adopts soluble polyamide ester precursor, solve insoluble polyimide and can not be prepared into porous-film or process complicated problems, can easily insoluble polyimide be prepared into the film with honeycomb structure, problems such as traditional polyamic acid precursor package stability and solubility property difference have been overcome, the polyimide kind that is suitable for is many, has greatly expanded the technology of preparing of polyimide porous membrane, the kind and the Application Areas of film;
(2) the present invention adopts the solution phase inversion process to prepare the polyamide ester precursor film, through progressively imidization of gradient increased temperature, can very easily air be introduced and make the polyimide porous membrane that inside has honeycomb structure in the polyimide matrix, be a kind of effective ways that reduce the polymide dielectric constant.The film that makes has porosity height (30-85%), the little characteristics such as (1.5-2.4) of specific inductivity.Can regulate the structure and the specific inductivity of final polyimide film easily by changing simple methods such as film preparation liquid concentration, coagulation bath composition and temperature;
(3) method provided by the invention can solve the problem with honeycomb structure polyimide film surface compact planarization difference, polyimide porous membrane two surface compacts that make are smooth, internal cellular structure is even, the film strength height, be difficult for to produce in the use subside, electric leakage or breakdown problem; Heat stability is good can be used for the high-power electric appliance element;
(4) procedure provided by the invention and equipment are simple, and cost is low, can make film continuously, and preparation efficiency improves greatly; Also can be directly with membrane prepare in electron device, realize the in-situ preparing of polyimide with ultra-low dielectric constant porous-film.
Description of drawings
Fig. 1 (a) is the electron scanning micrograph of (PMDA-ODA) polyimide film upper surface in the specific embodiment of the invention 1;
Fig. 1 (b) is the electron scanning micrograph of (PMDA-ODA) polyimide film lower surface in the specific embodiment of the invention 1;
Fig. 1 (c) is the electron scanning micrograph of (PMDA-ODA) polyimide film section in the specific embodiment of the invention 1;
Fig. 2 (a) is the electron scanning micrograph of (BTDA-ODA) polyimide film upper surface in the specific embodiment of the invention 9;
Fig. 2 (b) is the electron scanning micrograph of (BTDA-ODA) polyimide film lower surface in the specific embodiment of the invention 9;
Fig. 2 (c) is the electron scanning micrograph of (BTDA-ODA) polyimide film section in the specific embodiment of the invention 9.
Embodiment
Among the present invention, core is at first to prepare the polyamide ester precursor film with honeycomb structure, adopts progressively imidization mode of gradient increased temperature the polyamide ester precursor film to be converted into the ultra low dielectric constant polyimide membrane with honeycomb structure then.
Polyamide ester precursor film with honeycomb structure is a raw material with the soluble polyamide ester, adopt the preparation of solution phase inversion process, concrete steps are: polyesteramide is dissolved in polar organic solvent N, N-N,N-DIMETHYLACETAMIDE (DMAc), N obtain the preparation liquid that mass concentration is 15-30% in dinethylformamide (DMF) or the N-Methyl pyrrolidone (NMP); With preparation liquid after filtration, degassing back spreads to the liquid film that thickness is the 50-500 micron on the stainless steel supporter; Liquid film stopped to immerse in the 20-50 ℃ of precipitation bath behind the certain hour in air solidified 1-30 minute; Film after the curing obtains having the polyamide ester precursor film of honeycomb structure with ethanol or acetone soaking and washing after the drying.Described precipitation bath is water, ethanol or water and alcoholic acid mixed solution, and perhaps water and alcoholic acid mixed solution account for the mixed solution that 50-90%, above-mentioned solvent account for 10-50%.
The molecular structural formula of described polyesteramide is:
Wherein, Ar
1For:
Ar
2For:
R is :-CH
3(M) ,-CH
2CH
3(E) ,-(CH
2)
2CH
3(P) ,-(CH
2)
3CH
3(B) ,-C (CH
3)
3(t-B).Polyesteramide by the contriver according to document (Macromolecules, 1989,22,4477) and (Journal ofPolymerScience, Part A-1,1967,5,3043) method is synthetic in: tetracarboxylic dianhydride (as pyromellitic acid dianhydride (PMDA) or 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA)) at the small molecules monohydroxy-alcohol (as methyl alcohol (M), ethanol (E), n-propyl alcohol (P), the propyl carbinol (B) or the trimethyl carbinol (t-B)) in esterification generate two acid diesters, two acid diesters carry out polycondensation with diamines (as 4 (ODA) or p-phenylenediamine (PDA)) again and make polyesteramide after chloride.Use (Ar in this specification sheets
1-Ar
2RS) represent corresponding polyesteramide, as (PMDA-ODA ES) expression pyromellitic acid dianhydride/4 type polymeric amide ethyl ester.
By conditions such as change preparation liquid concentration, the liquid film residence time, coagulation bath composition and temperature, the structure that can regulate the polyesteramide film easily, and then control honeycomb size, porosity and specific inductivity in the final polyimide film.
The concentration of polyesteramide is one of principal element of final polyimide membrane structure of decision and specific inductivity in the preparation liquid, under the identical situation of other film forming condition, with the reduction of polyesteramide concentration, the honeycomb size increases in the polyimide film, porosity improves, specific inductivity reduces.
The polyesteramide liquid film is stopped appropriate time, can regulate the size of honeycomb size in the polyimide film, the residence time prolongs, and the honeycomb size in the polyimide film reduces, the porosity of film reduces, specific inductivity increases.
The thickness of liquid film is the principal element of the final polyimide film thickness of decision; The thickness of liquid film is by the degree of depth control of the scraper edge of a knife; In order to prepare the ultra low dielectric constant polyimide membrane of optimum thickness at the 40-100 micron, the optimum thickness of striking liquid film is the 200-400 micron.
The composition of precipitation bath and temperature are the important factor in order of final polyimide film honeycomb structure and specific inductivity, and solvent improves in the precipitation bath, and the honeycomb size reduces in the film; The content of water improves, and honeycomb size and porosity increase in the film, and the film specific inductivity reduces; Coagulation bath temperature raises, and the honeycomb size increases in the film, porosity reduces, specific inductivity increases.
Film after the curing soaks in ethanol or acetone, cleans, and the exchange of solvent in the precursor film is come out, and helps that it is follow-up in dry and imidization; Can adopt ultra-sonic oscillation to improve the efficient of removing solvent simultaneously, shorten scavenging period.
In order to prevent the oxidizing reaction in the imidization process, imidization is being carried out in nitrogen or argon gas atmosphere; In order to realize the stable of abundant imidization and membrane structure, adopt gradient increased temperature, the method for imidization progressively, promptly 150 ℃ following 1 hour, 220 ℃ following 1 hours, 350 ℃ are following 2 hours.
The ultra low dielectric constant polyimide membrane surface of preparation micropore or smooth degree occur when low, need carry out surface densification, planarizing process to the polyamide ester precursor film: the dilute solution that polyesteramide and solvent is mixed with 2-6%, then precursor film is soaked 20-40 second therein, take out after drying, identical in polyesteramide and solvent and the described preparation liquid; Perhaps, carry out surface densification, planarizing process again to handling the polyimide film that obtains: polyimide film is soaked 40-60 second in above-mentioned dilute solution through imidization, take out after drying and obtain the surperficial polyimide film of fine and close smooth polyesteramide layer that is, once more through the progressively imidization processing of described gradient increased temperature.
By to polyimide film honeycomb hole size, porosity and thickness measurement, sem observation pattern and specific inductivity are measured, the structure of characterization of membrane and dielectric properties.Among the present invention, the measuring method of polyimide membrane structure and dielectric properties is respectively:
Film surface and inner pattern: in liquid nitrogen, quench membrane sample disconnected, the metal spraying of using metal evaporation instrument (Hitachi E1020) to carry out surface, section is again handled, go up the section of observation film and the structure and morphology of upper and lower surface in scanning electronic microscope (SIRION-100, Holland) then.
The mensuration of the porosity of film and honeycomb mean pore size: adopt mercury injection apparatus (DEMO AutoPore9500, the U.S.) to measure.
Film thickness determination: adopt screw micrometer to measure, choose 5 measuring points and average.
Specific inductivity is measured: polyimide film is following dry 10 hours at 65 ℃, after removing surface water and other adsorbents, at 25 ℃ of specific inductivity of measuring membrane sample down with YD2810B type LCR digital electric bridge, adopting the diameter of electrode is 5 centimetres, every kind of polyimide film is chosen 5 sample determinations, with the specific inductivity of its mean value as this film.
Be ultra low dielectric constant polyimide membrane preparation method's embodiment below, every implementation condition is listed in the table, and the implementation step of all embodiment is all identical with aforementioned implementation step.
The soluble polyamide ester is synthetic for contriver's reference literature among the embodiment, and used main raw material has: PMDA: the SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS; BTDA: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS; ODA: Shanghai chemical reagents corporation of Chinese Medicine group; PDA: chemical reagent purchase and supply 5-linked chemical plant, Shanghai; DMF: Shanghai Jingwei Chemical Co., Ltd.; DMAc: Shanghai Jingwei Chemical Co., Ltd.; NMP: Shanghai San'aisi Reagent Co., Ltd.
Embodiment 1: the structure of every implementation condition and gained ultra low dielectric constant polyimide membrane and performance are as shown in Table 1.
Table one
Embodiment 2: the structure of every implementation condition and gained ultra low dielectric constant polyimide membrane and performance are as shown in Table 2.
Table two
Embodiment 3: the structure of every implementation condition and gained ultra low dielectric constant polyimide membrane and performance are as shown in Table 3.
Table three
Embodiment 4: the structure of every implementation condition and gained ultra low dielectric constant polyimide membrane and performance are as shown in Table 4.
Table four
Embodiment 5: the structure of every implementation condition and gained ultra low dielectric constant polyimide membrane and performance are as shown in Table 5.
Table five
Embodiment 6: the structure of every implementation condition and gained ultra low dielectric constant polyimide membrane and performance are as shown in Table 6.
Table six
Embodiment 7: the structure of every implementation condition and gained ultra low dielectric constant polyimide membrane and performance are as shown in Table 7.
Table seven
Embodiment 8: the structure of every implementation condition and gained ultra low dielectric constant polyimide membrane and performance are as shown in Table 8.
Table eight
Embodiment 9: the structure of every implementation condition and gained ultra low dielectric constant polyimide membrane and performance are as shown in Table 9.
Table nine
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (2)
1. the method for a preparing ultra low dielectric constant polyimide membrane by polyamide ester precursor phase transformation, it is characterized in that, polyesteramide is dissolved in polar organic solvent N, N-N,N-DIMETHYLACETAMIDE, N obtain the preparation liquid that mass percent concentration is 15-30% in dinethylformamide or the N-Methyl pyrrolidone; With preparation liquid after filtration, degassing back spreads to the liquid film that thickness is the 50-500 micron on the stainless steel supporter; The supporter that will have liquid film immerses in the precipitation bath and solidifies; With the film after solidifying with ethanol or acetone soaking and washing, obtain the polyamide ester precursor film after the drying, realize surface densification by the following method, planarizing process: polyesteramide and solvent are mixed with the dilute solution that mass percent concentration is 2-6%, the polyamide ester precursor film is soaked 20-40 second therein, take out after drying, in nitrogen or argon gas, obtain ultra low dielectric constant polyimide membrane through gradient increased temperature imidization processing, described precipitation bath is a water, ethanol or water and alcoholic acid mixed solution, perhaps to account for volume percent be 50-90% for water and alcoholic acid mixed solution, above-mentioned polar organic solvent accounts for the mixed solution that volume percent is 10-50%; Gradient increased temperature imidization treatment temp and time are: 150 ℃ following 1 hour, 220 ℃ following 1 hours, 350 ℃ are following 2 hours.
2. according to the method for the described a kind of preparing ultra low dielectric constant polyimide membrane by polyamide ester precursor phase transformation of claim 1, it is characterized in that the molecular structural formula of described polyesteramide is:
Wherein, Ar
1For:
Ar
2For:
R is :-CH
3,-CH
2CH
3,-(CH
2)
2CH
3,-(CH
2)
3CH
3Or-C (CH
3)
3
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| CN100532429C (en) * | 2007-12-10 | 2009-08-26 | 华南理工大学 | Method for preparing polyimide with ultra-low dielectric constant |
| CN103127845A (en) * | 2011-12-05 | 2013-06-05 | 杭州费尔过滤技术有限公司 | Polyamide microporous film without support and preparation method |
| CN104592756B (en) * | 2015-02-10 | 2017-03-01 | 中国电子科技集团公司第四十九研究所 | A kind of polyimides humidity-sensitive material and preparation method thereof |
| CN108329689B (en) * | 2018-03-08 | 2020-09-15 | 哈尔滨理工大学 | Low-dielectric-constant polyimide porous film and preparation method thereof |
| CN109912615A (en) * | 2019-03-20 | 2019-06-21 | 浙江福斯特新材料研究院有限公司 | Benzo alicyclic dianhydride and low dielectric coefficient polyimide precursor film |
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