TWI300162B - Positive-working alkaline developable photosensitive polyimide/clay nanocomposite compositions and preparation thereof - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type alkaline aqueous solution-developed photosensitive polyimine, which is particularly related to a low-stress positive-type alkaline aqueous solution-developed photosensitive polyimine. The prior art polyimine (polyimine, pi) is widely used in the semiconductor industry due to its excellent thermal stability and good mechanical, electrical and chemical properties, such as 1C wafer protective film, metal interlayer insulating material and Chip scale package (CSP) and the like. The ρι used in the IC process can be divided into the traditional PI and the photosensitive PI (hereinafter referred to as pspi). Conventional PIs must be used in conjunction with a photoresist to obtain the desired trace pattern. However, PSPI can be directly exposed to development and patterned. Since the use of PSPI simplifies the 1C process, reduces costs, and increases product yield, more and more 1C plants tend to use PSPI. When polyimine is used in the above applications, it is usually applied to a silene wafer or other substrate by a solution, and after drying and high temperature hardening, a film is formed on the substrate. When using this film process, polyimine produces internal stresses on the substrate. The main source of this internal stress is: solvent evaporation of the solution. 2. High temperature hardening of the polyaniline 3. The thermal expansion coefficient between the polyimide and the substrate is too large. When the polyimide is formed into a film, if the internal stress is too large, the substrate (such as a germanium wafer) may be bent or cracked, or delamination may occur, and the 1C element may be damaged. When the IC wafer size is getting larger and larger, 1300162, especially in the 12-inch wafer process, the problem caused by this internal stress is more significant, so it is more urgent to develop low-stress polyimine materials. To reduce the internal stress of the polyimide film, it can be started in three directions. The first method is to lower the hardening temperature of the polyimine. The second method is to introduce a soft group (e.g., siloxane) to the molecular structure of the polyimine to reduce its Y〇ung's modulus. The third method is to reduce the thermal expansion coefficient (hereinafter referred to as Cte) of the polyimine to be close to the thermal expansion coefficient of the substrate. A common method for reducing the thermal expansion coefficient of polyimine is to synthesize a linear, rigid-r〇d molecular structure via molecular design. However, this method involves the synthesis of new monomers, which is a time consuming and expensive method, and when formulated into PSPI, there may be a problem that it cannot be developed with an alkaline aqueous solution. Further, the coefficient of thermal expansion is lowered by the addition of a filler, but the amount added is too small to be easily dispersed, and it is easy to aggregate and affect the photosensitivity, making it difficult to process the fine pattern. There are many related literatures on the use of inorganic materials to modify polyimine, but they are only limited to the study of PI alone. Little research has been done on photosensitive polyimides. Photosensitive polyimine has recently been reported as follows. As shown in the table, Zhu

Zl_Kang et al. have published a series of siiica additions to photosensitive polyimides using the sol_gel method to form a photosensitive polyimide/cerium oxide mixture. 1300162 Title and properties of photosensitive polyimide/titania-silica hybrid Materials Science & Engineering, C: Biomimetic and Supramolecular Systems (2002), C22(l), 61_65 Preparation and properties of photosensitive polyimide/Si02 hybrid Gongneng Gaofenzi Xuebao (2000 ), 13(3), 325-328 Photosensitive polyimide/silica hybrids Advanced Materials (Weinheim, Germany) (2000), 12(14), 1055-1057 According to the experimental results of the aforementioned paper, the content of cerium oxide is 〇% The CTE is reduced by 25%, but there is agglomeration of the cerium oxide particles, which causes problems in exposure and development. SUMMARY OF THE INVENTION The present invention utilizes the technique of dispersing clay in a polymer material to develop a low-stress photosensitive polyimide/clay nano composite, which does not involve the synthesis of new polymers and monomers, due to clay in PI The medium is dispersed in nanometer, so it does not affect its sensitivity, so it is an economical and simple method. Since the nano-dispersed clay has a high surface to volume ratio, which limits the thermal expansion and contraction of the polymer, the thermal expansion coefficient of the polymer material can be effectively reduced. The low-stress photosensitive polyimide/clay nano composite material developed by the technology of nano-dispersed clay in polymer materials has a CTE reduced by 1300162 23% when the clay is added at 5%, and There is no problem with the lithography process. A positive-type photosensitive polyimide/clay nano composite composition disclosed by the present invention, comprising: a) testing raw water, valley liquid soluble polyamic acid; b) - a photosensitive dissolution inhibitor for inhibiting the alkaline water/liquid solution/complexity of polylysine, and the photosensitive dissolution inhibitor is decomposed after illumination, and is soluble in an aqueous test solution; c) An organic clay; and d) a solvent, wherein the photosensitive dissolution inhibitor b) is 5 6 G/ of the polyglycolic acid hook. And the modified organic clay is 1-30% by weight of the polyamic acid & Preferably, the polyamic acid a) has the following structure:

Where η is in the range ΐ〇_6〇〇; is _h

; X〇 is -Η or -OH group; Read ei fresh four-valent aromatic group, composed of: !300162

—0—, _s—, a C(CF3)2—C(CH2)2—, a CH2—, a S〇2—called sJHC〇—

Z a J, one or a 1

Z Z wherein z is H or C1_C4 alkyl, m = l_2〇;

Ah is one or more tetravalent aromatic groups selected from the group consisting of an aliphatic group, a heterocyclic group or a mixture thereof with the tetravalent aromatic group, the group having the following structure Composition of tetravalent aromatic groups··

彳3

9 1300162 Preferably, the photosensitive dissolution inhibitor b) is a diazoquinone compound having the following structural formula:

Wherein D can be a halogen atom (H) or any of the following compounds:

Preferably, the photosensitive dissolution inhibitor b) is 20% to 40% by weight of the polyamic acid a). Preferably, the modified clay c) is prepared by cation exchange of a layered structural mineral having a cation exchange capacity (CEC) of 50 to 300 meq/100 g with an amine group-containing compound. More preferably, the layered structure mineral is a clay having a cation exchange capacity of from 80 to 120 meq/100 g. The clay may be montmorillonite, saponite, beidellite, or mica; and the amine group-containing compound may be C6- having one or two amino acids or amine groups. The C18 alkane, wherein the clay 1300162 is Na+_montena and the amine group-containing compound is dodecylamine is preferred. Preferably, the solvent d is N-methyl-2-pyrrolidone; N,N-dimethylacetamide; DMAc), dimethylformamide (DMF), γ-butyrolactone (GBL), or a mixed solvent thereof. The present invention also provides a method for preparing a positive-type light-sensitive polyimide/clay nano composite composition, comprising mixing the polyamic acid a), the photosensitive dissolution inhibitor b) in the solvent sentence, and The modified organic clay c). The invention also provides a method for preparing a positive-type light-sensitive polyimine/clay nano composite composition, comprising dispersing the modified organic clay in the solvent d); and one or more diamine compounds Reacting with the one or more di- oxalic anhydrides in the dispersion to form the poly-proline acid a); and reacting the photosensitive dissolution inhibitor b) with the modified organic clay c) and polyglycine a) The mixture is mixed. Embodiments The photosensitive polyimine/clay nanocomposite composition developed by the positive alkaline aqueous solution of the present invention comprises a photosensitive polyimide precursor and an organic clay modified. The composition of the photosensitive polyimine precursor is a polyamic acid to which a photosensitive dissolution inhibitor is added. The clay is a hydrophilic; the bismuth salt layer structure, and most of the polymer is hydrophobic, and the clay is bonded to the high-segment gate lacking g, so the phase of the two-phase uniformity is reached 11 1300162 It is difficult, so it is necessary to modify the clay to make it an organic clay to increase its affinity with organic molecules. Commonly used clays such as montmorillonite, mica, etc. The cation exchange capacity (CEC) is 50-300 meq/100g. If the CEC is greater than 300 meq/100g, the ionic bond between the layers is too strong, which is not conducive to dispersion. If CEC is less than 50 meq/100g The modifiers adsorbed between the layers are insufficient, and the affinity between the polymer and the polymer is not good, and the dispersion is not good. Generally, the clay can be modified by a cation exchange method, and the binder is an amine-containing organic compound such as an amine. The 〇-modified organic clay such as primary acid, primary aliphatie amines, and quaternary ammonium salt can be scanned by X-ray diffraction analyzer to judge the clay layer and layer. Is the distance between increase. In general, a polymer/clay nanocomposite is produced by inserting a sandwiching agent into a clay layer to increase the interlayer distance, and then inserting and polymerizing the organic monomer or inserting the polymerized polymer to make the clay reach The nano-scale dispersion forms interclated nano composites or exfoliated nanocomposites. The organic clay modified by the present invention is uniformly dispersed in a solvent. The content of organic clay is 1%-7% of the total solid content, and the solvent can be N-methyl-2-pyrrolidone (hereinafter referred to as ΝΜΡ), Ν, Ν- N, N-dimethylacetamide (DMAc), dimethylformamide (DMF), γ-butyrolactone (GBL), 12 l3〇〇l62 or its mixed solvent. The polymerization of the photosensitive pi precursor (polyproline) is carried out in a dispersed organic clay dispersion by means of in-situ polymerization, or the polymerized polylysine which has been polymerized is added. The uniformly dispersed organic clay dispersion is uniformly mixed, and the photosensitive polyimide/clay nano composite composition can be obtained by the above method. The lithographic process of the photosensitive polyimide/clay nano composite composition is as follows: a. The photosensitive polyimide/clay nano composite composition is coated on a suitable substrate by ash coating or other means. ; b • pre-bake; c • exposure, d · development; and e · hard baked after the pattern is a polyimide / clay nano composite. In the above step (a), the positive-type photosensitive polyimide/clay nano composite composition is applied onto a suitable substrate, for example, a substrate. The above coating method is, for example, spin coating, roller coating, screen coating, curtain coating, dip bonding C〇ating) and spray coating, but are not limited to the above coating method. In the examples, the film formed by coating is prebaked at 7 Torr to 12 ° C for several minutes to evaporate the solvent therein. Then, the coated substrate is exposed to actinic radiation under a mask, such as X-ray, electron beam, ultraviolet, visible, or other sources that can be used as actinic rays. Wait. After the exposure, the coated substrate is subsequently developed by an alkaline aqueous developer, and then a photoresist pattern is obtained. The alkaline aqueous developer package 3 described above is, for example, an inorganic test (potassium hydroxide, sodium hydride), 13 1300162 primary amine (ethylamine), secondary amine (diethylamine), tertiary amine ( Triethylamine), tetramethylammonium hydroxide, preferably a developer containing a tetramethylammonium hydroxide component. Development can be accomplished by soaking, spraying or laminating or using other means of developing means. The developed photoresist pattern is then washed with deionized water and then subjected to a hard baking process at 250 to 400 ° C to convert the polylysine therein into a heat-resistant polyimide. Example

Na+-montmorilloniten (Monteigne stone): CEC=95 meq/100g, Baikang Ceramic Materials Co., Ltd., code PK802, chemical composition analysis (wt%): Ο: 49.06%, Si: 29.94%, Al: 12%, Na : 3.61%, Κ: 0.02%, Mg: 3.65%, Ca: 1.39%, Fe: 0.07%, Zr: 0.01%, Cr: 0.01%, Μη: 0.01%. Dodecylamine (DOA): 98%, ACROS Organics Co·Pyromellitic dianhydride (PMDA), Oxydiphthalic anhydride (Sf) ODPA), all purchased from Chriskev Co., was dried under vacuum at 150 ° C for 24 hours. 4,4'-Oxydiphenylamine (hereinafter, ODA) was purchased from Chriskev Co., and anhydrous NMP was purchased from Aldrich Co., and was used without purification. Photosensitive dissolution inhibitor 2,3,4-tris(1-oxo-2-heavy-Ci-I-5-contigyloxy)-dimercapto-ketone (2,3,4-tris(l-oxo-2) -diazonaphthoquinone-5-sulfonyloxy)- 1300162 Other drug benzophenone) was purchased from Koyo Chemicals under the designation PIC-3 from Aeros Co. and used directly without purification.

(PMDA)

Clay modification (the procedure for upgrading is shown in the figure). 1 lg of clay PK802 (CEC = 95 meq/l〇〇g) is added to an appropriate amount of deionized water and stirred to disperse. This is solution (1). b. Add DOA with twice the molar ratio to the clay to an appropriate amount of deionized water, and add hydrochloric acid to ionize 'this is the solution (2). 15 1300162 c. Pour the solution (1) into the solution (2), heat it to 8 (rc and vigorously mix for 3 hours) in an oil bath to ion exchange the clay with the (four) agent. The reaction formula is as follows: rnh2 + Hci —► rnh3+ cr

Na MONT + RNH3 + CT — ► RNH3 + MONT + NaCl d. After the reaction, the solution was repeatedly filtered and washed with deionized water to remove chloride ions until the solution was titrated with the AgNCh solution without white precipitate. e· The organic product is dried after vacuum drying at 80 C and then pulverized with a 325 meshi sieve. The original clay and the organic clay D0A_clay powder were powdered x_ray diffraction analyzer on the test piece at 20=2~15. XRD analysis was performed, and the xrd map is shown in Fig. 2. The value can be obtained from the XRD pattern and then substituted into the formula of 2d sin 0 - η λ to obtain the d value. It is the distance between the layers of clay. From the XRD analysis, the original clay was at 20=6·95. There is a broad x_ray crystal diffraction peak, which is contributed by the crystal plane of the 脱(Na) soil, and the corresponding interlayer distance is 12.7. The organic clay D〇A_ciay has a strong crystalline diffraction peak at =4.95°, and the corresponding interlayer distance is 18·〇Α〇. From the above results, it is known that the ionized agent is ionized with concentrated hydrochloric acid and with Na ions. After the ion exchange of montmorillonite, the intercalation agent does have Na+ which replaces the surface of the citrate layer between the silicate layers, and the unequal interlayer distance structure of the unmodified clay is opened. And the distance between the layers of 1300162 becomes a relatively uniform tantalate layer structure. Synthetic Polyimine Precursor 9.80 g (0.49 mole) of ODA and 94 ml of NMP were placed in a dry three-necked flask and stirred at room temperature under nitrogen until completely dissolved. 872 g again

(0·40 mole ) PMDA, 3.10 g (0.10 mole ) ODPA and 20 ml of NMP were added, and stirred under nitrogen and normal temperature for 6 hr to obtain a viscous poly-proline solution with an inherent viscosity (Inherent viscosity) (0· 5 g/dL) is 1 (dL/g). Preparation of positive aqueous solution developing photosensitive polyimide/clay nano composite composition The above-prepared polylysine solution (solid content: 16% by weight) 12·5 g 'NMP 4.2 g, prepared as described above Modified organic clay (D〇A-Clay) 0.06 g (3% by weight of polyamidamide), and PIC-3 photosensitive dissolution inhibitor 0.80 g (40% by weight of polyamide), evenly stirred evenly After that, it was filtered through a 5 μηι PTFE filter membrane, and subjected to a lithography imaging experiment. The lithography imaging experiment was carried out by coating the above-mentioned prepared photosensitive polyimide/clay nano composite composition in a yellow light chamber on a Shi Xi wafer by a spin coater, and baking it in an oven at 120 ° C for 5 min. Thereafter, exposure with an unnitered mercury arc lamp (wavelength range: 250-400 nm) was 300 mj/cm2, developed with a 0.3% TMAH aqueous solution, and finally washed with deionized water at 350 °C. Bake hard for 1 hour to obtain a polyimine pattern. Figure 3 17 1300162 is an enlarged view of its optical microscope. The UV-visible spectrum analysis of the above-mentioned prepared photosensitive polyimide/clay nanocomposite composition before and after exposure is shown in Fig. 4. It can be seen from Fig. 4 that after absorption of the composition of the present invention, the absorption peak between 35 〇 and 45 〇 Ilm disappears, and it is seen that the photosensitive dissolution inhibitor has a bleaching action to ensure that the underlying photoresist is also exposed. It can be clearly seen from the TEM image (Fig. 5) that the clay is delaminated and dispersed in the photosensitive polyimide. Figures 6 and 7 are the characteristic curves of the photosensitive polyimide precursors without added and added modified organic clay. Since the modified organic clay is dispersed in the polyamic acid solution, it is not micro The shadow process is hindered, so the characteristic curves of the two are similar. The photosensitive polyimine precursor without modified organic clay had a light sensitivity of 292 mJ/cm2 and a contrast of 1.83 (Fig. 6). The PI-sensitized formula with 3% clay added had a light sensitivity of 3〇1 mJ/cm2 and a contrast value of 1.66 (Fig. 7). The results of the coefficient of thermal expansion (CTE) test are shown in the table below. When the amount of modified organic clay added is 3%, the CTE has been greatly reduced. Modified organic/polyglycine (weight ratio) 0/100 3/100 5/100 7/100 % of PIC-3 based on the weight of poly-proline. 58.61 46.34 45.10 42.64 CTE change % 0% I 21 % I 23% \ 27% Therefore, the photosensitive polyimide/clay nano composite composition of the present invention can effectively reduce the thermal stress of the PI film. 18 1300162 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a block diagram of a upgrading process for a modified organic clay suitable for use in the present invention. Figure 2 is an x-ray diffraction pattern of the original clay and the modified organic clay D〇A-Clay powder, wherein the curve (a) is the original clay and the curve is the modified organic clay. Fig. 3 is an optical microscopic enlarged view of a polyimine pattern obtained by performing a lithographic imaging experiment using the photosensitive polyimide/clay nanocomposite composite of the present invention. Fig. 4 is a UV-visible spectrum diagram of a photosensitive polyimide/clay nano composite composition of the present invention before and after exposure, wherein curve A is before exposure and curve B is after exposure. Figure 5 is a transmission electron microscopy (TEM) using the photosensitive polyimide/clay nano composite of the present invention. Figure 6 is a photosensitive polyazide without modified organic clay. Characteristic curve of the amine precursor. Fig. 7 is a characteristic curve of a photosensitive polyimide precursor having an added modified organic clay.

Claims (1)

1300162 % 卜r. * Two picks, patent application scope: • A positive type of light-sensitive polyimide/clay nanocomposite composition, including:) Southern sorghum raw water> gluten-soluble polyamine (p〇lyamic acid); b) a photosensitive dissolution inhibitor for inhibiting the alkaline water solubility of poly-proline, and the photosensitive dissolution inhibitor decomposes after illumination, but is soluble in a base An aqueous solution; c) a modified organic clay; and b) a weight d) of the polyamic acid a) a polyamic acid a) / a granule, wherein the photosensitive dissolution inhibitor is 5-60%; And the modified organic clay is 1 - 30%, wherein the polyamic acid a) has the following structure: Wherein the target range of 11 is 1〇-6〇〇; X0 is 汨 or 〇 〇 · · ΑΓι is one or more kinds of tetravalent aromatic earth selected from the following groups" is a tetravalent aromatic group having the following structure :: Cheng Xiangji 20 1300162 (amended in March 2008) —〇—,一S—?—C(CF3)2—C(CH2)2—, a CH2—, a S02—, an NHCO- OO U- zz or and —(CH2)srSi—O—Si—( CH2)rtr·II zz wherein Z is H or C1-C4 alkyl, 1-20; Ar2 is one or more tetravalent aromatic groups selected from the group consisting of an aliphatic group or a heterocyclic group. a group or a mixture thereof with the tetravalent aromatic group, the group consisting of a tetravalent aromatic group having the following structure: 〇 21 |300162 (Amended in March 2008) The photosensitive dissolution inhibitor b) is a diazoquinone compound having the following structural formula·· Wherein D can be a hydrogen atom (H) or any of the following compounds: :and The modified clay c) is prepared by cation exchange of a layered structural mineral having a cation exchange capacity (CEC) of up to 300 meq/100 g with an amine group-containing compound. 2. The composition of claim 1, wherein the photo-sensitization inhibitor b) is from 20% to 40% by weight of the polyamido acid a). 3. The composition according to claim 1, wherein the layer is a clay having a cation exchange capacity of 80 to 120 meq/100 g 22 (as amended in March 2008); 1300162. 4. The composition of claim 1, wherein the clay is m〇ntmorillonite, saponite, beidellite, or mica; and the amine-containing The compound is a C6-C18 alkane having one or two amino acids or amine groups. 5. The composition of claim 4, wherein the clay is Na-quinone and the amine-containing compound is dodecylamine 〇6. The composition of the above, wherein the solvent d) is N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide; DMAc), dimethylformamide (DMF), gamma primetine (γ-bixtyrolactone; GBL), or a mixed solvent thereof. The method for preparing a positive-type photosensitive polyimide/clay nano composite composition according to the above-mentioned claim, comprising the poly-proline in the solution J d) a) the photosensitive dissolution inhibitor and the modified organic clay. Technique 8. A method for preparing a positive-type light-sensitive poly-West-Asian private/clay nano composite composition as described in claim 1 of the patent application, including the modification 23 • 1300162 (revised March 2008) The organic clay c) is dispersed in the solvent d); reacting one or more diamine compounds with one or more dicarboxylic anhydrides in the dispersion to form the polyamic acid a); and inhibiting the photosensitive dissolution The agent b) is mixed with a reaction mixture containing the modified organic clay c) and polyamic acid a). twenty four