CN105461924A - Preparation method for hyperbranched polymide film with low dielectric constant - Google Patents
Preparation method for hyperbranched polymide film with low dielectric constant Download PDFInfo
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- CN105461924A CN105461924A CN201511022160.7A CN201511022160A CN105461924A CN 105461924 A CN105461924 A CN 105461924A CN 201511022160 A CN201511022160 A CN 201511022160A CN 105461924 A CN105461924 A CN 105461924A
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- 238000002360 preparation method Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 30
- 229920001721 polyimide Polymers 0.000 claims description 72
- 239000004642 Polyimide Substances 0.000 claims description 67
- 239000000047 product Substances 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000010408 film Substances 0.000 claims description 46
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 239000005357 flat glass Substances 0.000 claims description 36
- 238000001291 vacuum drying Methods 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 239000012043 crude product Substances 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 14
- 239000006227 byproduct Substances 0.000 claims description 14
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 10
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 150000004984 aromatic diamines Chemical class 0.000 claims description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- CSNFMBGHUOSBFU-UHFFFAOYSA-N pyrimidine-2,4,5-triamine Chemical compound NC1=NC=C(N)C(N)=N1 CSNFMBGHUOSBFU-UHFFFAOYSA-N 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 229940100630 metacresol Drugs 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- -1 aromatic diamine acid anhydrides Chemical class 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- PLKZZSKEJCNYEQ-UHFFFAOYSA-N 4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=C(O)C=C1 PLKZZSKEJCNYEQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000004377 microelectronic Methods 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 4
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 abstract description 4
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012856 packing Methods 0.000 abstract 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- MPNBXFXEMHPGTK-UHFFFAOYSA-N pyrimidine-4,5,6-triamine Chemical compound NC1=NC=NC(N)=C1N MPNBXFXEMHPGTK-UHFFFAOYSA-N 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 7
- 108700009934 HBPI Proteins 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003808 methanol extraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XROLBZOMVNMIFN-UHFFFAOYSA-N 1-(1-benzofuran-4-yl)propan-2-amine Chemical compound CC(N)CC1=CC=CC2=C1C=CO2 XROLBZOMVNMIFN-UHFFFAOYSA-N 0.000 description 1
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000008208 nanofoam Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention relates to a preparation method for a hyperbranched polymide film with the low dielectric constant. A series of the low-dielectric constant PI films with a hyperbranched structure are synthesized by taking 2,4,6-triaminopyrimidine (TAP) as a branching center through a one-step method. Through introduction of the hyperbranched structure, the dielectric constant of the PI film is significantly lowered, the inherent advantages of PI are better kept, and the good mechanical strength and thermo-oxidative stability are supplied to the film. The hyperbranched structure contains a large quantity of molecular chain end groups, dense packing of molecular chains is effectively inhibited, and therefore the hyperbranched PI film has the excellent dissolution characteristic to be more prone to be processed into a complex device. Compared with a Kapton standard film which is generally used at present, under the same testing conditions, the dielectric constant of the hyperbranched PI film prepared through the method is lowered by 20%-40%, the lowest dielectric constant even gets close to 2.0 and reaches the ultralow dielectric constant level, and the urgent demand for micro-electronic industry development in future can be met.
Description
Technical field
The invention belongs to super-branched polyimide method for manufacturing thin film, be specifically related to a kind of super-branched polyimide method for manufacturing thin film with low-k.
Background technology
In information age today, along with developing rapidly of science and technology, electronic product is just towards multifunction, high performance and portable future development.In order to adapt to the demand of microelectronic industry, designing high performance super large-scale integration and seeming and become more and more important.Along with wiring density in unicircuit constantly increase, microprocessor size constantly reduces, between the signal delay that capacitance-resistance sluggishness (RCdelay) causes, line, the problem such as interference and power dissipation becomes increasingly conspicuous.The characteristic dimension of microelectronic device depends on the specific inductivity (Dk) of inter-metal dielectric in unicircuit.Original paper characteristic dimension is less, requires that corresponding dielectric Dk is lower.Therefore Development of New Generation has the dielectric substance of lower Dk is the problem that microelectronic needs solution badly.
Polyimide (PI) is widely used in electronic apparatus industry owing to integrating multiple excellent properties, but be limited by the fast development that its higher intrinsic Dk (3.0-3.8), PI still can not meet modern microelectronic industry to require (Dk<2.5).At present, the research of domestic and international academia to low-k PI is strengthened day by day, achieves many achievements attracted people's attention.Yang etc. are by a series of organic synthesis, and synthesized a kind of fluorine-containing dibasic acid anhydride TFDA newly, its structure as shown in Figure 1.By this novel monomeric and various diamine copolymerization with obtain a series of fluorine-containing PI.Fluorine-containing PI specific inductivity is minimum is down to 2.75 for such, and has excellent solvability (S.Y.Yangetal., J.Polym.Sci., PartA:Polym.Chem., 2004,42,4143-4152).Chio etc. adopt AHHFP, BTDA and 6FDA three kinds of monomers (corresponding chemical structure as shown in Figure 1) to prepare a series of fluorine-containing PI for raw material, when AHHFP/BTDA/6FDA mol ratio is 1/0.5/0.5, the Dk of prepared PI is minimum is down to 2.17 (S.Chioetal., J.Appl.Polym.Sci., 2010,117,2937-2945).But although introduce the specific inductivity that fluorine element significantly can reduce PI in PI skeleton, fluorine-containing PI self also has some shortcomings, on the one hand, only lean against in PI skeleton and introduce fluorine atom, the reduction limitation of PI specific inductivity, and the price of fluorochemical monomer is generally higher; On the other hand, in order to obtain lower specific inductivity, sacrifice some excellent properties of PI, the introducing of such as fluorine element causes the second-order transition temperature of PI and mechanical property reduction, thermal expansivity increase, creep-resistant property to decline, adhesion property is deteriorated etc., and these all have impact on the application of PI in microelectronics industry.
Consider that the Dk of air is close to 1, sight was transferred to the development aspect of porous PI material by investigator gradually in recent years.Chen etc. introduce the poor side chain of the thermostabilitys such as polyacrylamide, polymethylmethacrylate and polyvinyl alcohol-b-methyl methacrylate respectively on the main chain of PI by RAFT living polymerization, be evenly distributed eventually through the standby bore hole size of thermal destruction legal system, specific inductivity be about 2.0 porous PI film (Y.W.Chenetal., J.Mater.Chem., 2004,14,1406-1412).On the basis of forefathers, Chu etc. then by adding trifunctional monomer three amine pyrimidine (TAP) in reactant, the PI nanofoam materials with crosslinking structure has been prepared through polyester amine salt presoma process, further the specific inductivity of material is down to 1.77 (H.J.Chuetal., Polym.Advan.Technol., 2006,17,366-371).But many results of study show, porous PI film but significantly sacrifices thermal characteristics and the mechanical property of PI intrinsic excellence while obtaining low Dk, and many microvoid structures have at higher temperature line tendency of subsiding.Therefore, find a kind of cheapness, the method for PI film that easy preparation has low-k and excellent thermal and mechanical property concurrently is still a challenge in material science.
Software simulation shows, hyperbranched polymer macromolecule internal has many sub-nanometers to nano level cavity, these cavitys will play the role of " nanometer micropore ", thus make super-branched polyimide (HBPI) have the characteristic being similar to the low dielectric of porous PI.Simultaneously because nano level cavity does not have the compactness of havoc PI molecular structure, thus imparting HBPI is better than mechanical strength and the thermotolerance of porous PI.HBPI has a large amount of molecule chain ends simultaneously, thus presents excellent solubility property, gives the processibility that HBPI is good.
Summary of the invention
The technical problem solved
In order to avoid the deficiencies in the prior art part, the present invention proposes a kind of super-branched polyimide method for manufacturing thin film with low-k.
Technical scheme
A kind of step 1: add triaminopyrimidine TAP successively at reaction vessel, aromatic diamine, aromatic dibasic acid acid anhydride and high boiling solvent C, stirs and system is lowered the temperature under argon shield; The mol ratio of described aromatic diamine and triaminopyrimidine TAP is 0 ~ 5:1, and in system, the mol ratio of all amido functional groups and anhydride functional group is 1:1, and solid content controls at 20wt% ~ 30wt%;
Step 2: when system temperature is down to 0 ~ 10 DEG C, add catalyzer, stirs 4 ~ 10h under argon shield; The mol ratio of described catalyzer and aromatic diamine acid anhydrides is 0.1 ~ 1:1;
Step 3: system temperature is risen to 60 ~ 100 DEG C, stirs 2 ~ 6h under argon shield; System temperature is risen to 130 ~ 200 DEG C, under argon shield, stir 24 ~ 48h reaction terminate;
Step 4: when system is cooled to 25 DEG C, reaction solution is poured in solvent E and separate out solid product, obtain crude product after filtering;
Step 5: adopt solvent E to wash crude product 2 ~ 5 times, obtain product G; The volume of solvent for use E is 30% ~ 50% of solvent for use E volume in step 4;
Step 6: adopted by product G solvent E to extract 24 ~ 48h in apparatus,Soxhlet's, obtain product H; The volume of solvent for use E is 50% of solvent for use E volume in step 5;
Step 7: by product H dry 12 ~ 24h in vacuum drying oven, temperature controls, at 120 ~ 150 DEG C, to obtain product J;
Step 8: product J be dissolved in low boiling point solvent K, solid content controls at 4wt% ~ 10wt%; After adopting tetrafluoro filter element filtering, be cast in and be adjusted on the sheet glass of level in advance;
Step 9: sheet glass is placed 2 ~ 5h at 25 DEG C and is placed in vacuum drying oven, temperature controls at 50 ~ 100 DEG C, treatment time 10 ~ 20h;
Step 10: take out sheet glass after temperature is down to 25 DEG C, soaks after 24h through deionized water and takes off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Described aromatic diamine be in following several diamine any one or its combination, the chemical structural formula of aromatic diamine is as follows:
Described aromatic dibasic acid acid anhydride be in following several dibasic acid anhydride any one or its combination, the chemical structural formula of aromatic dibasic acid acid anhydride is as follows:
Described high boiling solvent C be in meta-cresol m-cresol, p-cresol p-cresol or ortho-cresol o-cresol any one or its combination.
Described catalyzer be in quinoline, isoquinoline 99.9 or phenylformic acid any one or its combination.
Described solvent E be in methyl alcohol, ethanol, n-propyl alcohol or Virahol any one or its combination.
Described low boiling point solvent K be in chloroform, methylene dichloride, tetrahydrofuran (THF) any one or its combination.
The volume ratio of described solvent E and high boiling solvent C is 5 ~ 10:1.
The aperture of the tetrafluoro filter core of described step 8 is 220nm.
Beneficial effect
A kind of super-branched polyimide method for manufacturing thin film with low-k that the present invention proposes, adopt 2,4,6 – Triaminopyrimidines (TAP) are Triamine monomer, prepare by single stage method the low dielectric HBPI film that solvability is excellent, thermotolerance is given prominence to, mechanical strength is high.The present invention have employed the triamino monomer TAP that amino activity differs in synthesis HBPI process, effectively prevent gelatin phenomenon, reduces production cost simultaneously, thus ensure that such PI film can better serve microelectronic industry.
The invention has the beneficial effects as follows: the present invention adopts a series of low dielectric PI film with dissaving structure of one-step synthesis method.The introducing of dissaving structure, significantly reduces the specific inductivity of PI film, maintains PI inherent advantages preferably simultaneously, imparts the good mechanical strength of film and thermo-oxidative stability.Comprise a large amount of molecule chain end base in dissaving structure, effectively inhibit the closely knit of molecular chain to pile up, thus make hyperbranched PI film have excellent dissolution characteristics, be easier to be processed to complex devices.Compared with the Kapton standard film generally used at present, under equal test condition, the specific inductivity of the hyperbranched PI film that legal system of the present invention is standby reduces 20% ~ 40%, lowest dielectric constant is even close to 2.0, reach the level of ultralow dielectric, the active demand of future microelectronics industry development can be met.
The invention has the beneficial effects as follows: the introducing of dissaving structure, significantly reduce the specific inductivity of PI film, maintain PI inherent advantages preferably simultaneously, impart the good mechanical strength of film and thermo-oxidative stability.Comprise a large amount of molecule chain end base in dissaving structure, effectively inhibit the closely knit of molecular chain to pile up, thus make hyperbranched PI film have excellent dissolution characteristics, be easier to be processed to complex devices.Compared with the Kapton standard film generally used at present, under equal test condition, the specific inductivity of the hyperbranched PI film that legal system of the present invention is standby reduces 20% ~ 40%, lowest dielectric constant is even close to 2.0, reach the level of ultralow dielectric, the active demand of future microelectronics industry development can be met.
Accompanying drawing explanation
Fig. 1: the chemical structure of several synthesizing imine monomer used
Fig. 2: the syntheti c route schematic diagram being low dielectric super-branched polyimide film
Fig. 3: the dielectric properties being super-branched polyimide film
Fig. 4: the dynamic mechanical properties being super-branched polyimide film
Fig. 5: the thermo-oxidative stability being super-branched polyimide film
Fig. 6: the mechanical strength being super-branched polyimide film
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Embodiment 1
0.8342g2 is added successively to being equipped with in churned mechanically reaction vessel, 4,6-Triaminopyrimidine (TAP), 2.9422gBPDA and 15g ortho-cresol, argon shield, open and stir and lower the temperature to system, when system temperature is down to 5 DEG C, add 0.25g quinoline, continue to stir 4h, then at 70 DEG C, react 3h, after system temperature risen to 140 DEG C of reaction 24h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 140mL methyl alcohol and separate out solid product, obtain crude product F after filtering.With 60mL methanol wash crude product F3 time, obtain product G.Product G is used 70mL methanol extraction 24h in apparatus,Soxhlet's, obtains product H.By product H dry 12h in vacuum drying oven, temperature controls, at 120 DEG C, to obtain product J; 1g product J be dissolved in 19g chloroform, via hole diameter is be cast in after the tetrafluoro filter element filtering of 220nm to be adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 3h by sheet glass and process 10h, temperature controls at 60 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Embodiment 2
0.4171g2 is added successively, 4,6-Triaminopyrimidine (TAP) to being equipped with in churned mechanically reaction vessel, 2.0526gBAPP, 2.9422ga-BPDA and 16g p-cresol, argon shield, opens and stirs and lower the temperature to system, when system temperature is down to 1 DEG C, add 0.4g isoquinoline 99.9, continue to stir 5h, then at 80 DEG C, react 4h, after system temperature is risen to 160 DEG C, reaction 30h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 130mL ethanol and separate out solid product, obtain crude product F after filtering.With 50mL washing with alcohol crude product F4 time, obtain product G.Product G is used 65mL extraction using alcohol 30h in apparatus,Soxhlet's, obtains product H.By product H dry 15h in vacuum drying oven, temperature controls, at 130 DEG C, to obtain product J; 2g product J be dissolved in 32g methylene dichloride, via hole diameter is after the tetrafluoro filter element filtering of 220nm, is cast in and is adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 4h by sheet glass and process 12h, temperature controls at 70 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Embodiment 3
0.5005g2 is added successively, 4,6-Triaminopyrimidine (TAP) to being equipped with in churned mechanically reaction vessel, 1.3371g6FBA, 3.1022gODPA and 12g meta-cresol, argon shield, opens and stirs and lower the temperature to system, when system temperature is down to 4 DEG C, add 0.5g phenylformic acid, continue to stir 7h, then at 85 DEG C, react 5h, after system temperature is risen to 180 DEG C, reaction 35h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 100mL n-propyl alcohol and separate out solid product, obtain crude product F after filtering.Wash crude product F5 time with 40mL n-propyl alcohol, obtain product G.Product G is extracted 35h with 50mL n-propyl alcohol in apparatus,Soxhlet's, obtains product H.By product H dry 18h in vacuum drying oven, temperature controls, at 140 DEG C, to obtain product J; 2g product J be dissolved in 45g tetrahydrofuran (THF), via hole diameter is after the tetrafluoro filter element filtering of 220nm, is cast in and is adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 5h by sheet glass and process 15h, temperature controls at 80 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Embodiment 4
0.3754g2 is added successively, 4,6-Triaminopyrimidine (TAP) to being equipped with in churned mechanically reaction vessel, 1.1674gOTDA, 3.2232ga-BTDA and 19g p-cresol, argon shield, opens and stirs and lower the temperature to system, when system temperature is down to 5 DEG C, add 0.7g quinoline, continue to stir 8h, then at 90 DEG C, react 5h, after system temperature is risen to 190 DEG C, reaction 40h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 150mL Virahol and separate out solid product, obtain crude product F after filtering.With 60mL washed with isopropyl alcohol crude product F3 time, obtain product G.Product G is used 75mL isopropanol extraction 40h in apparatus,Soxhlet's, obtains product H.By product H dry 20h in vacuum drying oven, temperature controls, at 140 DEG C, to obtain product J; 2g product J be dissolved in 40g chloroform, via hole diameter is after the tetrafluoro filter element filtering of 220nm, is cast in and is adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 4h by sheet glass and process 12h, temperature controls at 90 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Embodiment 5
0.2503g2 is added successively, 4,6-Triaminopyrimidine (TAP) to being equipped with in churned mechanically reaction vessel, 1.3879gDDM, 4.0231gHQDPA and 17g ortho-cresol, argon shield, opens and stirs and lower the temperature to system, when system temperature is down to 0 DEG C, add 0.25g quinoline, continue to stir 4h, then at 70 DEG C, react 3h, after system temperature is risen to 140 DEG C, reaction 24h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 140mL methyl alcohol and separate out solid product, obtain crude product F after filtering.With 60mL methanol wash crude product F3 time, obtain product G.Product G is used 70mL methanol extraction 24h in apparatus,Soxhlet's, obtains product H.By product H dry 12h in vacuum drying oven, temperature controls, at 120 DEG C, to obtain product J; 1g product J be dissolved in 19g chloroform, via hole diameter is after the tetrafluoro filter element filtering of 220nm, is cast in and is adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 3h by sheet glass and process 10h, temperature controls at 60 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Embodiment 6
0.2002g2 is added successively, 4,6-Triaminopyrimidine (TAP) to being equipped with in churned mechanically reaction vessel, 2.4338g6FMB, 4.0231gRsDPA and 20g p-cresol, argon shield, opens and stirs and lower the temperature to system, when system temperature is down to 1 DEG C, add 0.4g isoquinoline 99.9, continue to stir 5h, then at 80 DEG C, react 4h, after system temperature is risen to 160 DEG C, reaction 30h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 130mL ethanol and separate out solid product, obtain crude product F after filtering.With 50mL washing with alcohol crude product F4 time, obtain product G.Product G is used 65mL extraction using alcohol 30h in apparatus,Soxhlet's, obtains product H.By product H dry 15h in vacuum drying oven, temperature controls, at 130 DEG C, to obtain product J; 2g product J be dissolved in 32g tetrahydrofuran (THF), via hole diameter is after the tetrafluoro filter element filtering of 220nm, is cast in and is adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 4h by sheet glass and process 12h, temperature controls at 70 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Embodiment 7
0.5005g2 is added successively, 4,6-Triaminopyrimidine (TAP) to being equipped with in churned mechanically reaction vessel, 0.8492gDMBZ, 3.5828gDSDA and 15g meta-cresol, argon shield, opens and stirs and lower the temperature to system, when system temperature is down to 4 DEG C, add 0.5g phenylformic acid, continue to stir 7h, then at 85 DEG C, react 5h, after system temperature is risen to 180 DEG C, reaction 35h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 100mL n-propyl alcohol and separate out solid product, obtain crude product F after filtering.Wash crude product F5 time with 40mL n-propyl alcohol, obtain product G.Product G is extracted 35h with 50mL n-propyl alcohol in apparatus,Soxhlet's, obtains product H.By product H dry 18h in vacuum drying oven, temperature controls, at 140 DEG C, to obtain product J; 2g product J be dissolved in 45g chloroform, via hole diameter is after the tetrafluoro filter element filtering of 220nm, is cast in and is adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 5h by sheet glass and process 15h, temperature controls at 80 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Embodiment 8
0.3754g2 is added successively, 4,6-Triaminopyrimidine (TAP) to being equipped with in churned mechanically reaction vessel, 0.5948gPPD, 6.2844gFBDA and 19g p-cresol, argon shield, opens and stirs and lower the temperature to system, when system temperature is down to 5 DEG C, add 0.7g quinoline, continue to stir 8h, then at 90 DEG C, react 5h, after system temperature is risen to 190 DEG C, reaction 40h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 150mL methyl alcohol and separate out solid product, obtain crude product F after filtering.With 60mL methanol wash crude product F3 time, obtain product G.Product G is used 75mL methanol extraction 40h in apparatus,Soxhlet's, obtains product H.By product H dry 20h in vacuum drying oven, temperature controls, at 140 DEG C, to obtain product J; 2g product J be dissolved in 40g chloroform, via hole diameter is after the tetrafluoro filter element filtering of 220nm, is cast in and is adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 4h by sheet glass and process 12h, temperature controls at 90 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Embodiment 9
0.2503g2 is added successively, 4,6-Triaminopyrimidine (TAP) to being equipped with in churned mechanically reaction vessel, 1.7381gDDS, 2.1812gPMDA and 12g ortho-cresol, argon shield, opens and stirs and lower the temperature to system, when system temperature is down to 0 DEG C, add 0.25g quinoline, continue to stir 4h, then at 70 DEG C, react 3h, after system temperature is risen to 140 DEG C, reaction 24h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 90mL Virahol and separate out solid product, obtain crude product F after filtering.With 40mL washed with isopropyl alcohol crude product F3 time, obtain product G.Product G is used 45mL isopropanol extraction 24h in apparatus,Soxhlet's, obtains product H.By product H dry 12h in vacuum drying oven, temperature controls, at 120 DEG C, to obtain product J; 1g product J be dissolved in 19g chloroform, via hole diameter is after the tetrafluoro filter element filtering of 220nm, is cast in and is adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 3h by sheet glass and process 10h, temperature controls at 60 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
Embodiment 10
0.2002g2 is added successively, 4,6-Triaminopyrimidine (TAP) to being equipped with in churned mechanically reaction vessel, 2.2218g1,3,4-APB, 4.4424g6FDA and 20g p-cresol, argon shield, opens and stirs and lower the temperature to system, when system temperature is down to 1 DEG C, add 0.4g isoquinoline 99.9, continue to stir 5h, then at 80 DEG C, react 4h, after system temperature is risen to 160 DEG C, reaction 30h; After reaction terminates, when system is cooled to 25 DEG C, reaction solution is poured in 130mL methyl alcohol and separate out solid product, obtain crude product F after filtering.With 50mL methanol wash crude product F4 time, obtain product G.Product G is used 65mL methanol extraction 30h in apparatus,Soxhlet's, obtains product H.By product H dry 15h in vacuum drying oven, temperature controls, at 130 DEG C, to obtain product J; 2g product J be dissolved in 32g methylene dichloride, via hole diameter is after the tetrafluoro filter element filtering of 220nm, is cast in and is adjusted on the sheet glass of level in advance.Be placed in vacuum drying oven at 25 DEG C of placement 4h by sheet glass and process 12h, temperature controls at 70 DEG C.After temperature be down to 25 DEG C, take out sheet glass, soak after 24h through deionized water and take off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
By the visible the present invention of embodiment with triaminopyrimidine (TAP) for branch centers, adopt a series of low dielectric PI film with dissaving structure of one-step synthesis method.The introducing of dissaving structure, significantly reduces the specific inductivity of PI film, maintains PI inherent advantages preferably simultaneously, imparts the good mechanical strength of film and thermo-oxidative stability.Comprise a large amount of molecule chain end base in dissaving structure, effectively inhibit the closely knit of molecular chain to pile up, thus make hyperbranched PI film have excellent dissolution characteristics, be easier to be processed to complex devices.Compared with the Kapton standard film generally used at present, under equal test condition, the specific inductivity of the hyperbranched PI film that legal system of the present invention is standby reduces 20% ~ 40%, lowest dielectric constant is even close to 2.0, reach the level of ultralow dielectric, the active demand of future microelectronics industry development can be met.
Claims (9)
1. there is a super-branched polyimide method for manufacturing thin film for low-k, it is characterized in that step is as follows:
Step 1: add triaminopyrimidine TAP successively at reaction vessel, aromatic diamine, aromatic dibasic acid acid anhydride and high boiling solvent C, stir and system lowered the temperature under argon shield; The mol ratio of described aromatic diamine and triaminopyrimidine TAP is 0 ~ 5:1, and in system, the mol ratio of all amido functional groups and anhydride functional group is 1:1, and solid content controls at 20wt% ~ 30wt%;
Step 2: when system temperature is down to 0 ~ 10 DEG C, add catalyzer, stirs 4 ~ 10h under argon shield; The mol ratio of described catalyzer and aromatic diamine acid anhydrides is 0.1 ~ 1:1;
Step 3: system temperature is risen to 60 ~ 100 DEG C, stirs 2 ~ 6h under argon shield; System temperature is risen to 130 ~ 200 DEG C, under argon shield, stir 24 ~ 48h reaction terminate;
Step 4: when system is cooled to 25 DEG C, reaction solution is poured in solvent E and separate out solid product, obtain crude product after filtering;
Step 5: adopt solvent E to wash crude product 2 ~ 5 times, obtain product G; The volume of solvent for use E is 30% ~ 50% of solvent for use E volume in step 4;
Step 6: adopted by product G solvent E to extract 24 ~ 48h in apparatus,Soxhlet's, obtain product H; The volume of solvent for use E is 50% of solvent for use E volume in step 5;
Step 7: by product H dry 12 ~ 24h in vacuum drying oven, temperature controls, at 120 ~ 150 DEG C, to obtain product J;
Step 8: product J be dissolved in low boiling point solvent K, solid content controls at 4wt% ~ 10wt%; After adopting tetrafluoro filter element filtering, be cast in and be adjusted on the sheet glass of level in advance;
Step 9: sheet glass is placed 2 ~ 5h at 25 DEG C and is placed in vacuum drying oven, temperature controls at 50 ~ 100 DEG C, treatment time 10 ~ 20h;
Step 10: take out sheet glass after temperature is down to 25 DEG C, soaks after 24h through deionized water and takes off film, and at 150 DEG C vacuum-drying 24h, obtain the hyperbranched PI film of low dielectric.
2. there is the super-branched polyimide method for manufacturing thin film of low-k according to claim 1, it is characterized in that: described aromatic diamine be in following several diamine any one or its combination, the chemical structural formula of aromatic diamine is as follows:
3. there is the super-branched polyimide method for manufacturing thin film of low-k according to claim 1, it is characterized in that: described aromatic dibasic acid acid anhydride be in following several dibasic acid anhydride any one or its combination, the chemical structural formula of aromatic dibasic acid acid anhydride is as follows:
4. there is the super-branched polyimide method for manufacturing thin film of low-k according to claim 1, it is characterized in that: described high boiling solvent C be in meta-cresol m-cresol, p-cresol p-cresol or ortho-cresol o-cresol any one or its combination.
5. there is the super-branched polyimide method for manufacturing thin film of low-k according to claim 1, it is characterized in that: described catalyzer be in quinoline, isoquinoline 99.9 or phenylformic acid any one or its combination.
6. there is the super-branched polyimide method for manufacturing thin film of low-k according to claim 1, it is characterized in that: described solvent E be in methyl alcohol, ethanol, n-propyl alcohol or Virahol any one or its combination.
7. there is the super-branched polyimide method for manufacturing thin film of low-k according to claim 1, it is characterized in that: described low boiling point solvent K be in chloroform, methylene dichloride, tetrahydrofuran (THF) any one or its combination.
8. there is the super-branched polyimide method for manufacturing thin film of low-k according to claim 1 or 6, it is characterized in that: the volume ratio of described solvent E and high boiling solvent C is 5 ~ 10:1.
9. there is the super-branched polyimide method for manufacturing thin film of low-k according to claim 1 or 6, it is characterized in that: the aperture of the tetrafluoro filter core of described step 8 is 220nm.
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