Novel Photosensitive Polyimide Precursor Based on Polyisoimide

Chapter 19

Novel Photosensitive Polyimide Precursor Based on Polyisoimide Using Nifedipine as a Dissolution Inhibitor Downloaded by UNIV OF MICHIGAN ANN ARBOR on February 18, 2015 | http://pubs.acs.org Publication Date: May 5, 1995 | doi: 10.1021/bk-1994-0579.ch019

1

1

1

Amane Mochizuki , Tadashi Teranishi , Mitsuru Ueda , and Toshihiko Omote 2

1

Department of Materials Science and Engineering, Faculty of Engineering, Yamagata University, Yonezawa 992, Japan Central Research Laboratory, Nitto Denko Corporation, 1—1—2 Shimohozumi, Ibaraki 567, Japan

2

A new photosensitive polyimide precursor based on polyisoimide (PII) and nifedipine (DHP) as a photoreactive compound has been developed. PII was prepared by thering-openingpolyaddition of 4,4'hexafluoroisopropylidenebis (phthalic anhydride) (6FDA) and 4,4'hexafluoroisopropylidenebis(p-phenyleneoxy) dianiline (BAPF), followed by treatment with trifluoroacetic anhydride-triethylamine (TEA) in N-methyl-2-pyrrolidone (NMP). The dissolution behavior of the PII film containing 20 wt% of DHP after exposure and post-exposure bake (PEB) has been studied and we found that DHP in the unexposedPIIfilmacts as a dissolution inhibitor in DMAc after PEB at 150 °C. The photogenerated product in the exposedPIIfilm does not affect the dissolution rate. Because of this change in solubility, PII containing DHP functioned as a photosensitive resist. The resist had a sensitivity of 450 mJ/cm and a contrast of 2.5 when postbaked for 10 min at 150 °C and developed with DMAc. 2

Photosensitive polyimides are currently receiving considerable attention for their potential use in the fabrication of semiconductor devices and multichip modules, since they enable the number of process steps to be reduced by avoiding the use of classical photoresists. In most cases, the photosensitive groups are attached to the pendant carbonyl groups of poly(amic acid)s (polyimide precursor). A typical example is the acrylate ester of poly(amic acid) which after exposure to UV radiation results in a crosslinked polyimide precursor (/). After removing the unexposed polymer, the crosslinked photoreactive groups are thermolyzed during curing to leave polyimide. Positive resists based on a novolak resins with o-diazonaphthoquinone (NQD) are standard materials used in semiconductor manufacturing, where NQD acts as a dissolution inhibitor for aqueous base development of the novolac resin. Upon exposure to light, NQD is converted to indenecarboxylic acid that increases the dissolution rate of the novolac matrix in the regions where exposure has occurred. Nifedipine [ 1,4-dihydro-2,6-dimethyl-4-(nitrophenyl)-3,5-pyridinedicarboxylic acid dimethylester] (DHP) is well known not only as a Ca-antagonist but also as a photosensitive compound, and is converted to a corresponding pyridine derivative after exposure to UV light (eq.l) (2-3). 0097-6156/94/0579-0242$08.00/0 © 1994 American Chemical Society

In Polymeric Materials for Microelectronic Applications; Ito, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1995.

Downloaded by UNIV OF MICHIGAN ANN ARBOR on February 18, 2015 | http://pubs.acs.org Publication Date: May 5, 1995 | doi: 10.1021/bk-1994-0579.ch019

19. MOCHIZUKI ET AL.

Novel Photosensitive Polyimide Precursor243

The photochemical transformation in eq.(l) has been utilized in a photoresist formulation (4-5). Recently, Omote et al (6). reported that nifedipine acts as the dissolution inhibitor in a poly(amic acid) after post-exposure bake (PEB). This system exhibits good sensitivity and contrast. In a previous paper (7) we studied the preparation and properties of polyisoimide (PII) as a polyimide precursor. This investigation revealed that the solubility of PII in organic solvents is higher than that of corresponding polyimide. The isomerization reaction of isoimide to imide is catalyzed by an acid or a base, and PII is converted easily to polyimide by high temperature thermal treatment without the elimination of volatile compounds. These findings prompted us to develop a new positive resist by using PII and DHP as the polymer matrix and the photosensitive compound, respectively. This paper describes the preparation and properties of a novel positive photoreactive polyimide precursor consisting of PII and DHP.

Experimental Materials. Cyclohexanone, Ν,Ν-dimethylacetamide (DMAc), N-methyl-2pyrrolidone (NMP), and triethylamine (TEA) were purified by distillation. 4,4'Hexafluoroisopropylidenebis(p-phenyleneoxy)dianiline (BAPF) was purified by recrystallization from cyclohexane and chloroform. 4,4'-Hexafluoroisopropylidenebis (phthalic anhydride) (6FDA) was obtained from American Hoechst Co. Other reagents and solvents were obtained commercially and used as received. Nifedipine was synthesized according to the reported procedure (6). Polymer (PII) synthesis. A solution of BAPF (2.22 g, 5.0 mmol) in NMP (43.2 mL) was cooled with an ice-water bath. To this solution, 6FDA (2.59 g, 5.0 mmol) was added with constant stirring. The mixture was stirred at room temperature for 4 h. The resulting viscous solution was diluted with NMP (48.2 mL) and TEA (1.4 mL, 10.0 mmol) was added dropwise while continuously stirring. Then, the reaction mixture was cooled with an ice-water bath, and trifluoroacetic anhydride (1.54 mL, 11.0 mmol) was added dropwise with stirring. The mixture was stirred at room temperature for 4 h and poured into 2-propanol (1000 mL). The polymer precipitated was filtered off and dried in vacuo at 40 °C. The yield was 4.54 g (98 %). The inherent viscosity of the polymer in DMAc was 0.42 dL/g at a concentration of 0.5 g/dL at 30°C. IR (KBr): ν 1800 cm" (C=0), 930 cm" (C-O). Anal. Calcd for (C 6 H 2 N 0 F12) η : C, 59.62% ; H, 2.39% ; N, 3.02%. Found : C, 59.44% ; 2.70% ; N, 3.03%. 1

1

4

2

2

6



244

POLYMERIC MATERIALS FOR MICROELECTRONIC APPLICATIONS

Measurements. Infrared spectra were recorded on a Hitachi 1-5020 FT-IR spectrophotometer. Viscosity measurements were carried out by using an Ostwald viscometer at 30 °C. Thermal analyses were performed on a Seiko SSS 5000-TG/DTA 200 instrument with a heating rate of 10 °C/min for thermogravimetric analysis (TGA) and a Seiko SSS 5000 DSC220 using a heating rate of 10 °C/min for differential scanning calorimetry (DSC) under a nitrogen atmosphere. Molecular weights were determined using a gel permeation chromatograph (GPC) calibrated with polystyrene using a JASCO HPLC system equipped with a Shodex KD-80M column at 40 °C in dimethylformamide (DMF). Film thicknesses were measured on a Dektak 3030 system (Veeco Instruments Inc.) Dissolution rate. PII was dissolved at 15 wt% in cyclohexanone, to which was added DHP (5-50 wt% of the total solid). Films spin-cast on NaCl plates or silicon wafers were prebaked at 80 °C for 10 min and exposed through a filtered super high pressure mercury lamp SH-200 (Toshiba Lighting & Technology Corporation). Imagewise exposure was carried out in a contact mode. Exposed films were postbaked at 80-220 °C for 10 min and subjected to IR measurement or developed with DMAc at room temperature. Photosensitivity. Five- μηι thick PII films on silicon wafers were exposed to 436 nm wavelength light from the filtered super high mercury lamp. Exposed films were postbaked at 150 °C for 10 min and developed for 30 sec in DMAc at room temperature. The characteristic curve was obtained by plotting a normalizing film thickness against logarithmic exposure energy. Result and Discussion. Polyisoimide (PII) Synthesis. The polyisoimide (PII) based on 6FDA and BAPF was selected as the polymer matrix, because PII was expected to display excellent solubility characteristics in organic solvents as a result of ether and hexafluoroisopropyliden linkages in the polymer backbone. In a previous paper (7), we showed that trifluoroacetic anhydride-TEA was a suitable dehydrating agent for the formation of isoimides from amic acids. Thus, PII was prepared by the ring-opening polyaddition of 6FDA and BAPF, followed by treatment with trifluoroacetic anhydride-TEA in NMP (eq.2). The polymer structure was confirmed to be the corresponding PII by means of infrared spectroscopy and elemental analysis. The IR spectra exhibited a characteristic absorptions at 1800 cm due to the isoimide carbonyl. Imide contents determined by IR spectroscopy were less than 5%. Elemental analysis also supported the formation of expected polymer. PII was soluble in a wide range of organic solvents, such as DMAc, DMF, cyclohexanone, dichloromethane, toluene, acetone, and tetrahydrofuran. A transparent yellow films were cast from a DMAc or cyclohexanone solution of PII. The molecular weight ofjhe polymer having an inherent viscosity of 0.42 dL/g was determined by GPC. Mn and Mw values were 47,000 and 157,000, respectively, relative to standard polystyrene, and Rw/Rn was 3.3. The thermal stability of the polymer was examined by TGA. The polymer showed a 10% weight loss at 530 °C in nitrogen. DSC on the polymer powder showed an endotherm at 215 °C and a large exothermic peak at around 270 °C in the first heating process. In the second heating process, these peaks were not observed and new endothermic peak appeared at 245 °C. Furthermore, no weight loss was observed at around 270 °C. Based on these data, the first endotherm at 215 °C and the large exothermic peak at around 270 °C observed in the first heating process are assigned to the glass transition temperature -1




(Tg) and the thermal isomerization temperature of PII, respectively. The endothermic peak at 245 °C in the second heating process reflects Tg of the final polyimide (PI).

Ο

C - N Ar


Η

Η

Η !

HOOC

Dehydrating Agent

2

w

Ο

Ar,-N

Ο

Polyisoimide (PII)

Poly(amic acid)

ο

ο

Λ Λ

Isomerization "

ArfN

Ar,

π ο

(2)

N-f

π ο

Polyimide (PI) Ar,

Ar^ CF

3

ι

CF,

6FDA

BAPF

Lithographic Evaluation. It is very important to clarify the dissolution behavior of exposed and unexposed areas to produce satisfactory resist images. Thus, the PII film (5 μπι thick) containing 20 wt% of DHP was exposed (500 mJ/cm ) to 436 nm UV irradiation. The dissolution rate as calculated from the remaining film thickness after development with DMAc is shown as a function of PEB temperature in Figure 1. The dissolution rate of the exposed film is obviously faster than that of the unexposed film at PEB temperature below 170 °C. However, raising the PEB temperature above 170 °C reversed the dissolution behavior and the unexposed part became more soluble relative to the exposed part. In order to further investigate the dissolution behavior described above, PII films containing 20 wt% of DHP and no DHP were spin-coated on silicon wafers. These films were then heated to temperatures ranging from 80 to 150 °C for 10 min. Subsequently, the dissolution rates of the polymer films in DMAc were evaluated. Figure 2 indicates that the dissolution rate of unexposed PII containing DHP decreases markedly at approximately 130 °C compared to that of PII without DHP. However, exposed PII (500 mJ/cm ) films containing 20 wt% of DHP had a solubility almost identical to that of PII itself. Figure 3 shows the dissolution behavior of PII itself, PII containing DHP baked at 150 °C for 10 min, and PII containing DHP postbaked at 150 °C for 10 min after UV exposure (500 mJ/cm ), respectively. PII containing DHP after exposure and PEB had a comparable solubility in DMAc to PII itself and dissolved more than 10 times faster than the thermally treated PII containing DHP. These results indicate that thermally treated DHP acts as a dissolution inhibitor in the PII film whereas exposed DHP does not promote the dissolution rate. Similar behavior has been observed for the resist system composed of poly(amic acids) containing DHP. Omote et al (6). interpreted that the dissolution inhibition of poly(amic acids) as promoted by DHP near the PEB conditions results from decreased 2

2

2


246



10

3

F

io° I 100

ι

ι

I

150

200

250

PEB temperature (*C) Figure 1 Relationship between PEB temperature and dissolution rate.


19. MOCHÏZUKI ET AL.


hydrophilicity caused by intermolecular hydrogen bonding between DHP =NH and polymer -COOH groups. Furthermore, as one of the reasons for the dissolution promoting effect of DHP after exposure and PEB, the decrease of photochemical product, 4-(2'-nitrosophenyl)-2,3-dicarboxymethyl-3,5-dimethylpyridine (NDMPy), by vaporization has been proposed. To confirm the vaporization of NDMPy, the quantities of photogenerated NDMPy in the films exposed to 500 mJ/cm of 436 nm irradiation and subsequently heated at 150 °C for 10 min were measured by high performance liquid chromatography (HPLC). About 40 % of the NDMPy was actually vaporized out of the film. Thesefindingsclearly indicate that post-baking at 150 °C facilitates evaporation of NMDPy. Based on these results, the dissolution inhibition of DHP in DMAc by simple thermal treatment could be explained in terms of the formation of strong hydrogen bonds between DPH =NH groups and carbonyl groups of PII. The fact that the exposed polymer film had the same dissolution rate as PII itself could be explained as follows; (a) as photogenerated NMDPy does not have any active hydrogens, hydrogen bonds between NMDPy and PII can not be formed and (b) significant amounts of NMDPy evaporatefromthe film. On the other hand, the solubility of exposed PII gradually decreased with increasing PEB temperature. Polyisoimide isomerizes easily to the corresponding polyimide by high temperature thermal treatment and the isomerization reaction of isoimide to imide is also catalyzed by an acid or a base. To elucidate the reversed dissolution behavior, the isomerization ratio of PII to polyimide (PI) in the presence of DHP before and after exposure versus PEB temperature was measured. PII films containing 20 wt% of DHP, spin-coated on NaCl plate, were exposed (500 mJ/cm ) to 436 nm UV irradiation. The conversion of PII to PI was determined by comparing the absorptions of imide (1380 cm" ) with an internal standard peak at 1500 cm . The result is represented as a normalized value because PII included approximately 5% of the imide form (Figure 4). Although, there is no remarkable difference on the conversion of PII to PI between the exposed and unexposed films below 170 °C of PEB temperature, at a PEB temperature of 200 °C the exposed film isomerized much faster than the unexposed film. Therefore, the reversed dissolution behavior at higher PEB temperatures may be interpreted with the formation of PI catalyzed by photochemical product, NDMPy, which is a weak base. Table I shows the results of qualitative solubilities of exposed and unexposed PII films containing DHP after postbaking at 150 °C. Exposed polymer films exhibited excellent solubility toward various solvents as compared to the unexposed polymer. The effect of the DHP loading on the dissolution rate of PII in DMAc was studied as shown in Figure 5. About 10 wt% of DHP to polymer was enough to achieve a satisfactory dissolution contrast. After a preliminary optimization study involving DHP loading, postbaking temperature, and developer temperature, we formulated a photosensitive resist consisting of PII and 20 wt% of DHP. The sensitivity curve for a 5 μπι thick resist shown in Figure 6 is resulting from consistent with the dissolution behavior study. This indicates that the resist can be imaged at 450 mJ/cm with a contrast of 2.5. In Figure 7(a) are presented scanning electron micrographs of positive images made from PII containing 20 wt% of DHP by postbaking at 150 °C for 10 min exposure of 450 mJ/cm . This resist is capable of resolving 10 μηι features. Furthermore, the positive image of PII is converted to the positive image of PI by heating at 280 °C for 1 h without any deformation as indicated in Figure 7(b).


2

2

1

-1

2

2

Conclusion We have prepared a new positive-type photosensitive polyimide precursor by using polyisoimide as a polymer matrix and DHP as a photoreactive compound. The resist In Polymeric Materials for Microelectronic Applications; Ito, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1995.

248


J

10


PII only 10

Exposed PII

2

1

10

l

10

PII with DHP

I

I

I

I

Process Figure 3 Dissolution contrast for the system of PII and DHP.




Table I.


PEB Solubility Characteristics of Exposed and Unexposed PII Films containing DHP

Solvents

solubility Exposed

Cyclohexanone Acetone Methyl ethyl ketone Isoamyl acetate Dioxane 1,1,2,2,-Tetrachloroethane Chloroform 1,2-Dichloroethane Dimethyl acetamide Dimethyl formamide 2-Methoxy ethanol 2-Propanol Methanol 10% TMAH

Unexposed ±

++ ++ ++ ++ ++ ++ ++

4-

+ ± ± ± ± ±

++ ++

±

-

-

—

±

±

+ + : soluble at room temperature , + : soluble by heating , ± : partially soluble or swelling , — : insoluble


250


J

10

Ί

1

1

1

Exposed Ό

-θ-

~


ε c

10^

u G

©

S

Unexposed ίο

10

1

ϋ

10

20 30 40 DHP contents (%)

60

50

Figure 5 Relationship between DHP content and dissolution rate.

-τ

R

1

1

Γ

-

1

1

1

I

0

c

.a 0.8

J

0.6

μ

I o.4 ε

μ

ο 0.2 0 10

10

J

Exposure Dose ( mj/ cm ) Figure 6 Characteristic exposure curve for the system of PII and DHP.



MOCHIZUKI ET AL.

Novel Photosensitive Polyimide Precursor

Figure 7(a) Scanning electron micrographs of Pattern made from PII containing DHP (after development with DMAc).

Figure 7(b) Scanning electron micrographs of Pattern madefromPII containing DHP (after thermal treatment at 280 °C for 1 h).


252


is designed such that polyisoimide and D H P provide a soluble polyimide precursor and a photoreactive dissolution inhibitor, respectively. U n l i k e poly(amic acids), polyisoimides do not eliminate volatile compounds upon conversion to the final polyimide and, thus, represent a much more desirable polyimide precursor.


Acknowledgment The authors are indebted to Hitoshi Nagasawa and Sadao Kato for their technical assistance and Takeyoshi Takahashi for performing the elemental analyses. W e also wish to acknowledge the financial support from the Ministry o f Education, Science and Culture o f Japan (No.05453140).

Literature Cited 1. Rubner, R.; Ahne, H.; Kühn, E.; Koloddieg, G. Photogr. Sci. Eng., 1979, 23(5), 303 2. Berson, J. Α.; Brown, E. J.Am.Chem.Soc., 1955,77 , 447 3. Yamaoka, T.; Watanabe, H.; Koseki, K.; Asano, T. J.Imaging Sci., 1990,34 , 50 4. Ranz, E. Japan Patent Disclosure, kokai 49-60733 5. Leuschner, R.; Ahne, H.; Marquardt, U.; Nickel, U.; Schmidt, E.; Sebald, M.; Sezi, R. Microelectronic Enginieering ., 1993, 21, 255 6. Omote, T.; Yamaoka, T. Polym. Eng. Sci., 1992, 32(21), 1634 7. Mochizuki, Α.; Teranishi, T.; Ueda, M. Polym.J., 1994, 26, 315 RECEIVED September 13, 1994


Novel Photosensitive Polyimide Precursor Based on Polyisoimide

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