INT. J. NEW. INN.

, 2012, 1(2), 278-283

Review paper
ISSN:2277-4459

REVIEWING GENERAL CHEMICAL ETCHING BEHAVIOUR OF ENGINEERING POLYMER Kapton-H

Vimal Mehta1*, D. Shikha2, R P Chauhan3
1

Department of Physics, Maharishi Markandeshwar University, Mullana(Ambala), Haryana, India. 2 Department of Physics, Ambala College of Engineering, Mithapur(Ambala), Haryana, India. 3 Department of Physics, NIT, Kurukshetra, Haryana, India.

Abstract: Considering the important role played by engineering polymer Kapton-H in various fields, an attempt has been made to understand the general chemical etching behaviour of this polymer. The parameter reviewed is the thickness of polymeric sample studied by various workers with etching under different conditions. This paper is an attempt to find out the effect of various parameters like temperature, irradiation, polarization, annealing, etchant and light on the surface chemical etching behaviour of Kapton-H. Bulk-etch rates (Vb) and the bulk activation energies (Eb) are being reported as these are very important parameters for the surface chemical properties of a polymer. These studies are very useful for industrial optoelectronic applications of Kapton-H, as desired application can be made available if we know the etching parameters. These studies are also important as Kapton-H has unique properties which are essential for the production of more efficient and useful nuclear track filters. Keywords: Kapton-H, Bulk Etch Rate, Irradiation, Activation Energy

1. Introduction Polyimides (PIMs) are being utilised for a wide range of applications in a number of widely differing fields, namely aerospace, microelectronics, electro-photography, high-quality electrical insulation, etc [1]. PIMs, are the class of heterocyclic polymers, having an enviable set of desirable traits such as high tensile strength; good dielectric properties; high chemical stability, excellent thermal and thermo-oxidative properties; and good radiation tolerance. The chemical etching behaviour of polymer surfaces has been reported by many workers [2-4]. The study has played a major role [2, 6] in the development of micro-pore nuclear track detectors. Surface chemical etching behaviour under different physical conditions is also important for the application of engineering polymers in microelectronics and other transducer devices [4]. The surface chemical etching behaviour of Kapton- H polyimide has been studied by many groups [4, 7-8]. A detailed investigation of its surface chemical activity with the various etchants is required in field of electronics where the subtraction of material is done through chemical etching process. Laser etching, which is faster than chemical etching, can also be done as reported by Moskowitz et al. [9] but is applicable only where etching is required at very small area. For the development of nuclear track filters (NTF) a detailed investigation of the surface chemical etching behaviour of irradiated polymer is required. Considering the enormous applications of this engineering polymer Kapton-H in various fields, a detailed 278

investigation about its general chemical etching behaviour is required. The surface chemical behaviour is studied by the etching process. The bulk-etch rates (Vb) information, of course, is only one of the parameters that is very important and must be known for the different applications such as controlled production of pores in an NTF. This paper is an attempt to find out the effect of various parameters like temperature, irradiation, polarization, annealing, etchant and light on the surface chemical etching behaviour of Kapton-H using the data available in the literature. Bulk-etch rates (Vb) and the bulk activation energies (Eb) are also being reported. The bulk-etch rates (Vb) and the bulk activation energies (Eb) reported for 80 MeV/nucleon Ni ion irradiated Kapton-H has not been reported earlier. Similarly the bulk activation energies (E b) reported for 75 MeV/nucleon O+ ions irradiated Kapton-H has not been reported earlier. 2. Materials and methods Polymers are a large class of materials consisting of many small molecules (called monomers) that can be linked together to form long chains, thus they are known as macromolecules [10]. These are the substances with very high molecular mass each molecule of which consists of a very large number of simple structural units joined together in a regular manner (Greek, poly = many; mer = unit). Polymers are the backbone of modem civilization. Soon after the discovery of polymeric materials it became evident that they were quite sensitive to radiation of all INTERNATIONAL JOURNAL OF NEW INNOVATIONS

Review paper Mehta et al. __________________________________________________________________________________________ INT. J. NEW. INN., 2012, 1(2), 278-283 kinds. Chemical and structural degradation was observed first after the illumination with light and UV irradiation, and later with gamma rays and energetic charged particles such as electrons and ions. Production of well-defined parallel pores in polymer foils by ion irradiation and subsequent etching found the various applications in various fields. They are essentially applied as high-quality filters e.g. in purification of chemicals for pharmaceutical and electronic industries. Highly transparent ion -irradiated polymers are used for the construction of waveguides and other optical devices by suitably modifying the optical refractive index via ion irradiation. In conclusion, ion irradiation of polymers has become a wide field. Polyimides, coatings are used in a variety of interconnect and packaging applications, including passivation layers and stress buffers on integrated circuits multichip modules. The polyimide Kapton is available in two types-type H and type F. It is synthesized by a polycondensation reaction between an aromatic tetrabasic acid and an aromatic amine. Type F has a base coated with Teflon FEP fluorocarbon resins, whereas type H has polyimide film as base and is poly (4, 4' oxydiphenylene pyromellitimide). Kapton H has been used in the production of better nuclear track filters (NTFs) because of its unique properties as mentioned by Zhu et al. [11-12]; Vater et al. [13-14]; Guo et al. [15]; and Ganz et al. [16]. 2.1 Kapton-H Polyimides constitute an important class of materials because of their many desirable characteristics viz. excellent mechanical properties, low dielectric constant , low relative permittivity, high breakdown voltage, low dielectric loss over a wide range of frequency, good polarization, good processing capability, wear resistance, radiation resistance, inertness to solvents, good adhesion properties, low thermal expansion, good hydrolytic stability and long term stability. Because of these traits, polyimides have found applications in a host of technologies as intermetal dielectric, high temperature adhesive, photoresist etc. the applications of polyimides range from aerospace to microelectronics besides optoelectronics and composites. The synthesis of an aromatic polyimide was first reported in 1908 but it was not until the late 1950s that DuPont developed a successful commercial route to high molecular weight polyimide. DuPont introduced the first commercial polyimide in the late 1960s.since then the field has blossomed and there has been a high tempo of R & D activity in synthesizing an array of polyimides with requisite properties for a given application and in devising new methods of characterization. The oxydianiline (ODA) - pyromellitic dianhydride (PMDA) polyimide, with a commercial name Kapton-H, attracted the attention of researchers over other polyimides because ether structure of ODA would enhance possibilities for a moulding resin. Soon it was discovered that the ODA based polymers had real potential for moulding, superior toughness and hydrolytic stability as compared to other polyimide which were MPD (m-phenylene diamine) and PPD (p-phenylene diamine) based. Therefore Kapton-H polyimide, which is superior to other polyimides, has been used in the present investigations. Poly(4-4' oxydiphenylene pyromellitimide), chemical name of Kapton-H , is available in thin film form in standard thickness of 7.5, 12.5 ,25 ,50 ,75 and 125 polymer comprising of heterocyclic rings linked together by one or more covalent bonds. 2.1.1Synthesis Polyimides are produced by synthesizing the soluble polymer precursor namely poly (amic acid) and converting it to the final polyimide. Polyamic acid, prepared by the polycondensation of PMDA and ODA in N-methylpyrrolidinone (NMP), reacts by condensation cyclization to form an imide. This highly elegant process made it possible to bring the first significant commercial polyimide product into the market and it is still the method of choice in majority of applications. 2.1.2 Important properties Kapton-H exhibits marvelous electrical, dielectric, physical and mechanical properties retainable over a wide range of frequency and temperature, extending from 4 K to 600 K. The electrical properties include high resistivity, low dielectric loss over a wide frequency range and fairly high dielectric strength. It shows no glass transition degradation up to 600k. In addition, the material is resistant to radiation damage to a large extent and is hardly affected by various kinds of chemicals .There is no known organic solvent for the material. It is infusible and flame resistant. The Kapton-H polyimide (chemical name: poly 4-4' Oxydiphenylene Pyromellitimde, PMDA-ODA) used in the present study was procured from DuPont in film form. This polymer is well known for its outstanding electrical properties, solvent resistance, abrasion resistance, flame resistance and exceptional heat resistance. It has a monomeric unit of composition (C22H10N2O5) possessing the rigid chain structure. Figure1 represents the structural unit of Kapton-H polyimide. Pristine Kapton-H (C22H10N2O5) is a linear polymer comprising of heterocyclic rings linked together by one or more covalent bonds. Its chain assumes a plane zigzag conformation with an oxygen ether angle of 1260. Conformational analysis indicates that this is the most probable conformation of an isolated chain and would therefore exist in the amorphous as well as in crystalline phase. Figure 1 represents the molecular structure of repeating unit for Kapton-H.

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Review paper Mehta et al. __________________________________________________________________________________________ INT. J. NEW. INN., 2012, 1(2), 278-283
O C N C O C O O C N O

n n
Figure 1 In the polyimide crystal, the chain assumes a planer zigzag conformation, with an oxygen ether angle of 126 0. Conformational analysis indicates that this is the most probable conformation of an isolated chain and would, therefore, exist in the amorphous as well as in crystalline phase. The driving force for this conformation as well as for the remarkable stability of the film is the maximum degree of electron delocalization of the overlapping pieorbital, with resultant energy stabilization. The films are largely amorphous, having an as received crystallinity of 5%. These results are also in conformity with Laue transmission. A degree of ordering lower than the three dimensional crystallinity i.e. paracrystalline nature of Kapton-H was also found. The paracrystalline ordering in Kapton-H was confirmed by the increase in density from 1.418 to 1.424 gm cm-3 and crystallinity from 5% to 9% following annealing of the films at 2400C for 24 hours. The outstanding thermal resistance of the material can be assigned to (a) strong interchain forces (b) the conformational flexibility of the pyromellitic acid , diimide units and phenyl groups, which can oscillate in phase with the equivalent groups of the surrounding chains without a sensible loss of packing energy. The imide bonds in its aromatic heterocyclic structure cause the excellent mechanical properties and thermo- oxidative stability. 2.2 Methodology Pristine Kapton-H (4-4'-oxydiphenylene pyromellitimide) available from Dupont (U.S.A.) in the form of thin film of different thicknesses was used by different workers. The parameter reviewed is the bulk etch rate of polymeric sample with etching under different conditions as reported by various workers. The effect of various parameters like temperature, irradiation, polarization, annealing, etchant and light on the surface chemical etching behaviour of Kapton-H is being reviewed. Bulk activation energies (Eb) are also reported as this is very important parameter for the surface chemical properties of a polymer. 3. Result and Discussion 3.1 Effect of polarization For understanding the effect of induced polarization on surface chemical etching behaviour of Kapton-H polyimide, the test pieces are being polarized. The samples

can be prepared by subjecting the specimen fitted in a specimen holder and kept in a specially prepared temperature controlled furnace to the desired dc field at a certain constant temperature for some (1 hr - 1.5 hr). The polarization of the sample can also be done at different values of polarizing temperature. The specimen then can be cooled to room temperature within few minutes in the presence of field. Then both the pristine and the polarized samples are employed in etching process with the help of a chemical like NaOH, NaOCl etc. Quamara [7] reported the effect of polarization on the etching behaviour in NaOCl solution at 55 0C temperature. He reported that no significant change is observed in the etching rate of polarized sample with as- received sample, in fact there is net decrease in the etch rate with increasing polarizing temperature. The net decrease in the etch rate with increasing polarizing temperature can be attributed due to increase in magnitude of polarization. As induced polarization in polymers is linked with the increase in intermolecular forces and increased crystallinity due to orientation of molecules. Both Bhardwaj et al. [17] and Quamara et al. [18] reported that the electret nature of Kapton-H shows both the presence of strong dipolar as well as space charge relaxations. Therefore a poled Kapton-H sample will have more resistance towards chemicals owing to its enhanced inter-molecular forces resulting in an overall decrease in the etch rate. 3.2 Effect of heat treatment For understanding the effect of heat treatment on surface chemical etching behaviour of Kapton-H polyimide, the test pieces are given some heat treatment and then subjected to etching. Quamara [7] reported the effect of heat treatment on the etching behaviour in NaOCl solution at 55 0C temperature. He reported an increase in bulk etch rate in heat treated samples for sample treatment temperatures higher than 80 0C. The increase in bulk etch rate can be attributed due to loss of absorbed water as result of the given heat treatment (above 100 0C) as reported by both Bhardwaj et al. [17] and Quamara et al. [18]. The water molecule is bound to a carbonyl group and/or to ether-oxygen of polyimide chain as reported by Melcher et al. [19]. 3.3 Effect of light For understanding the effect of light on surface chemical etching behaviour of Kapton-H polyimide, the test pieces are subjected to etching under no light and with light exposed condition. Chakarvarti and Mahna [8] reported the etching behaviour of Kapton-H using NaOCl (4% Cl, w/v) at 30C under no-light and with light-exposed conditions. They reported that Kapton-H show linear etch rates when etched under no-light, whereas under light-exposed conditions it

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Review paper Mehta et al. __________________________________________________________________________________________ INT. J. NEW. INN., 2012, 1(2), 278-283 tend to approach saturated etch rates. The average bulketch rates reduces under light exposure to ca 50% of the value obtained under no-light conditions. This happens due to the oxidizing nature of the NaOCl which is sensitive to light that causes photo-reduction. Because the photoreduction process in NaOCl damages the etchant quality by reducing the basic nature of the solution, the etch rates are decreased. 3.4 Effect of etchant 1 Chakarvarti and Mahna [8] reported the surface chemical etching behaviour of Kapton-H polyimide subjected to two different etchants. The etching was done at 60 0C without stirring under no light condition with NaOCl (4% Cl, w/v) and NaOC1 + Ethanol (1:1) mixture respectively. They reported an enhancement in the etch rates by factors of ca 5 in the case of etching in NaOC1 + Ethanol (1:1) mixture in comparison to NaOCl (4% Cl, w/v). Garg et al. [20] also reported the dependence of etching mechanism of Kapton-H on the nature of the etchant. They reported the etching behaviour in two different etchants viz. NaOH and NaOCl. The etching of Kapton-H with NaOH proceeds with the formation of carboxylate salt and amino phenylene oxide whereas with NaOCl a complex salt formation is taking place. 3.5 Effect of etchant concentration For understanding the effect of etchant concentration on surface chemical etching behaviour of Kapton-H polyimide, the test pieces are subjected to etching in a same etchant, at same temperature but with different etchant concentration. Garg et al. [20] and Shikha et al. [21] reported the chemical etching behaviour of Kapton-H at 40 0C and at 50 0 C in 3N NaOH and 4N NaOH respectively. Table 1 shows the values of average bulk etch rate for the Kapton-H polymer. From the table 1 it can be said that with the increase in etchant concentration the values for average bulk etch rate also shows some increase. This may be due to the fact that once the etching starts more etchant concentration leads to the ease in etching of the polymer and hence more average bulk etch rate. 3.6 Effect of temperature For understanding the effect of temperature on surface chemical etching behaviour of Kapton-H polyimide, the test pieces are subjected to etching in a same etchant, but at different temperatures. Mehta et al [22] reported the etching of Kapton-H in 2N NaOH at two different temperatures 40 0C and 50 0C with same other etching conditions. The data provided by Mehta et al. [22] is used to produce Figure 2 that gives the average bulk etch rates for the Kapton-H as 4.3 2 40 0C 50 0C 40 0C 50 0C 3N NaOH 4N NaOH m/h and 7.5 m/h for 40 0C and 50 0C respectively. This data is not reported previously. Table 1: Effect of etchant concentration and temperature on average bulk etch rate S. N o. Temperature Etchant used Average Bulk etch rate (Vb) in m/h 1.31 3.46 3.20 8.30 Reference

Garg et al. [20] Shikha et al. [22]

Figure 2 shows a substantial increase in the average bulk etch rate of the polymer with the increase of temperature. This increase in average bulk etch rate with the increase in temperature can be attributed to the increase in solubility of carboxylate salt during the reaction of NaOH with Kapton-H and cleavage of O-carboxyamide bonds at temperatures above 40C [23]. 3.7 Effect of irradiation For understanding the effect of irradiation on surface chemical etching behaviour of Kapton-H polyimide, two test pieces one pristine and other irradiated are subjected to etching in a same etchant. Shikha et al. [21] reported the effect of irradiation by subjecting the irradiated Kapton-H (with 75 MeV/nucleon O+ ion beam of fluence 1.875 x 1012 ions/cm2) and pristine Kapton-H to etching in 4N NaOH under same conditions. Mehta et al. [22] also reported the effect of irradiation by subjecting the irradiated Kapton-H (with 80 MeV/nucleon Ni+ ion beam of fluence 2.7 x 1012 ions/cm2) and pristine Kapton-H to etching in 2N NaOH under same conditions. Mehta et al. [22] and Shikha et al. [21] reported that the general nature of the etching characteristics of irradiated samples appears almost similar to that of pristine sample. Shikha et al. [21] reported that etching is fast in the irradiated sample than in pristine in the begining but after some time interval it shows a decrease. The similar kind of behaviour is reported by Mehta et al. [22]. The etching process in irradiated samples depends upon two things an increase in average bulk etch rate due to breaking of some linkages leading to an ease in the chemical reaction and a decrease in etch rate due to the increase in the crystallinity of the sample [24-25].The initial increase in etch rate of the irradiated samples suggest the dominance of the breaking of imide linkages and a decrease in the etch rate in later stage suggests an increase in the crystallinity of the sample. The average bulk etch rates are 3.2 m/h and 3.6 m/h at 40 0C and 8.3 m/h and 9.6 m/h at 50 0C for pristine and O+ ion irradiated Kapton-H respectively as reported by Shikha et

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Review paper Mehta et al. __________________________________________________________________________________________ INT. J. NEW. INN., 2012, 1(2), 278-283 al. [21]. The data provided by Mehta et al. [22] is used to The average bulk etch rates are 4.3 m/h and 4.6 m/h at produce Figure 3 that gives the average bulk etch rates for the 40 0C and 7.5 m/h and 8.2 m/h at 50 0C for pristine and pristine and Ni+ ion irradiated Kapton-H at two temperatures Ni+ ion irradiated Kapton-H respectively. The bulk activation 40 0C and at 50 0C. energy (Eb) values are calculated using the data given by Mehta et al [22]. The bulk activation energy (E b) values for Temperature Average bulk etc rate the pristine and irradiated samples are calculated using the 40 C 4.2 m/h 50 C 7.5 m/h equation. [a]
0 0

25

Vb = A exp (-Eb/kT)
20

Thickness Removed (m)

15

10

0 0 50 100 150 200 250 300

Where A is a constant that depends upon the nature of the material, k is Boltzmann's constant and T is the temperature in K. The Eb is found to be 0.712 eV for pristine Kapton-H sample and 0.661 eV for irradiated Kapton-H sample. The activation energy is found to be less in the case of irradiated sample confirms the faster etching process after irradiating the sample.
Time (min)

4. Conclusion

This paper reports the effect of various parameters like Figure 2: average bulk etch rate of the Kapton-H at two temperature, irradiation, polarization, annealing, etchant different temperatures. and light on the surface chemical etching behaviour of Kapton-H as these are very important parameters for the Sample Average bulk etc rate surface chemical properties of a polymer. These studies are Pristine 4.3 m/h Irradiated 4.6 m/h very useful for industrial optoelectronic applications of 20 Kapton-H, as desired application can be made available if we know the etching parameters.

Thickness Removed (m)

15

[a]
10

References
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[2]
0 50 100 150 200 250 300

Time (min)

[3] [4]

26 24 22

Sample Average bulk etc rate Pristine 7.5 m/h Irradiated 8.2 m/h

[5] [6]
[b]

Thickness Removed (m)

20 18 16 14 12 10 8 6 4 20 40 60 80 100 120 140 160 180 200

[7] [8]

[9]

Time (min)

[10]

Figure 3: [a] average bulk etch rates for the pristine and Ni + [11] ion irradiated Kapton-H at 40 0C. [b] average bulk etch rates for the pristine and Ni+ ion irradiated Kapton-H at 50 0C.
[12]

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INT. J. NEW. INN., 2012, 1(2), 278-283

Review paper
ISSN:2277-4459

[13] P. Vater, T. -C. Zhu, S. Heise, R. Brandt and J. Vetter,GSI Sci. Rep. (1988), pp. 243. [14] P. Vater, R. Brandt and E. Bischoff, GSI Sci. Rep. 1988, 256. [15] S. L. Guo, M. Ganz, M. Fuest, P. Vater and R. Brandt, GSI Sci. Rep. (1988) pp. 255. [16] M. Ganz, C. D. Zhao, P. Vater and R. Brandt, GSI Sci. Rep. (1989) pp. 233. [17] R. P. Bhardwaj, J. K. Quamara, K. K. Nagpaul & B. L. Sharma, Phys Status Sold (a) 77 (1983) pp. 347. [18] J. K. Quamara, P. K. C. Pillai & B. L. Sharma, Acta Polymerica, 33, (1982) pp. 205-208. [19] J. Melcher, Y. Daben & G. Arlt, IEEE Transaction on Electrical Insulation, 24 (1989) pp. 31-38.

[20] Maneesha Garg, Anu Sharma, J. K. Quamra, Indian J pure & Appl Phys, 44 (2006) pp. 66-70. [21] D. Shikha, V. Sharma, J. K. Sharma and S. Kumar, Optoelectronics and Advanced Materials Rapid Communications. Vol. 3, No. 8, (2009), pp. 839-844. [22] V. Mehta, S. Kumar and J. K. Sharma, Optoelectronics and Advanced Materials Rapid Communications. Vol. 3, no. 3, (2009), pp. 265-269. [23] C.E. Diener and J. R. Susko, Polyimide, Vol. 1, edited by K. L. Mittal, Plenum Press, New York, (1982) pp. 353. [24] Manisha Garg & J. K. Quamara, Nucl Instrum Meth B, 179 (2001) pp. 83-88. [25] J. K. Quamara, Maneesha Garg and T. Prabhavathi, Thin Solid Films, 449 (2004) pp. 242-247.

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