Main physical properties of wide band gap semiconductor materials at 300 K.
Polyimides (PIs) are advanced polymeric materials well-known for their excellent thermal, electrical, mechanical and chemical properties . PIs are particularly attractive in the microelectronics industry due to their high thermal stability (
It is possible to observe that the semiconductor materials own a low coefficient of thermal expansion (CTE) below 6 ppm/°C. Thus, among the criteria for the PI passivation material choice, the CTE,
The classical poly(4,4’-oxydiphenylene pyromellitimide) (PMDA-ODA) appears as not well adapted for a severe thermal cycling operation due to the strong mismatch between its CTE (30-40 ppm/°C) and the one of semiconductor materials (<6 ppm/°C). This mismatch induces strong mechanical stresses in PMDA/ODA films coated on Si wafer (29 MPa). The poly(4-4’-oxydiphenylene biphenyltetracarboximide) (BPDA-ODA), the poly(4-4’-oxydiphenylene benzophenonetetracarboximide) (BTDA-ODA), the poly(
On the contrary, PIs synthesized from pyromellitic dianhydride (PMDA) or 3,3’,4,4’-biphenyltetracarboxilic dianhydride (BPDA) with
In this chapter, a particular attention is focused on the electrical properties of unaged BPDA-PDA and their evolution during a thermal aging on Si wafers in both oxidative and inert atmospheres. A comparative aging study with higher CTE’s PIs (PMDA-ODA and BPDA-ODA) is carried out in order to highlight the longer lifetime of BPDA-PDA. Prior to this, a paragraph dealing with the optimization of the thermal imidization of BPDA-PDA is reported through a simultaneous analysis of the infrared spectra and the electrical properties evolutions as a function of the imidization curing temperature. Finally, an application of BPDA-PDA to the passivation of SiC semiconductor devices will be presented through the PI on-wafer etching process and the electrical characterization of bipolar diodes at high temperature and high voltage.
2. Synthesis and optimization of the imidization of BPDA-PDA polyimide
The final physical properties of PIs and their integrity during aging depend strongly on the control and on the optimization of the imidization reaction (i.e. the curing process) [17,18]. This process step appears as crucial for industrial applications. Unfortunately, it is quite difficult to predict
2.1. Material, sample preparation and curing process
BPDA-PDA PI was purchased as a polyamic acid (PAA) solution. It was obtained through the two-steps synthesis method from its precursor monomers . The PAA solution was obtained by dissolving the precursor monomers in an organic polar solvent N-methyl-2-pyrrolidone (NMP). Two different vicosity types of the PAA solution were used for controlling the thickness. To convert PAA into PI, the solution was heated up to remove NMP and to induce the imidization through the evaporation of water molecules. Figure 1 shows the synthesis steps of BPDA-PDA.
The PAA solution was spin-coated on both square stainless steel substrates (16 cm2) and highly doped 2’’ Si N++ wafers (<3×10-3 Ω cm). PAA was first spread at 500 rpm for 10 seconds followed by a spin-cast at different rotation speeds between 2000 rpm and 4000 rpm for 30 seconds. Two successive curing steps followed the coatings. After a soft-bake (SB) at a low temperature (
The imidization cure is necessary to drive off solvent (boiling point of 202 °C for NMP), and to achieve the conversion of the PAA into PI by the formation of the imide rings. PAA coatings were hard-cured at
2.2. Optimization of the imidization reaction
2.2.1. Fourier transform infrared spectroscopy (FTIR)
In order to detect the chemical bond changes during the imidization of PAA into PI, assignments of the absorption bands in FTIR spectra are necessary to identify the amide and imide peaks. The characteristic IR absorption peaks were assigned thanks to previous works [17,26-36]. Usually, PAA spectra are compound of the N–H stretch bonds at 2900–3200 cm-1, the C=O carbonyl stretch from carboxylic acid at 1710–1720 cm-1, the symmetric carboxylate stretch bonds at 1330–1415 cm-1, the C=O carbonyl stretch of the amide I mode around 1665 cm-1, the 1540–1565 cm-1 amide II mode and the 1240–1270 cm-1 band due to the C–O–C ether aromatic stretch (if present in the monomer).
After the conversion reaction, the absence of the absorption bands near 1550 cm-1 (amide II) and 1665 cm-1 (amide I) indicates that PAA has been converted into PI. Simultaneously, this is confirmed by the occurrence of the C=O stretch (imide I) peaks at 1770–1780 cm-1 (symmetric) and 1720–1740 cm-1 (asymmetric), the typical C–N stretch (imide II) peak around 1380 cm-1, the C–H bend (imide III) and C=O bend (imide IV) absorption bands respectively in the ranges of 1070–1140 cm-1 and of 720–740 cm-1. The presence in PI films of a large absorption band between 2900 and 3100 cm-1 is associated to the C–H stretch bonds. Finally, the measurements may highlight the occurrence of a shoulder on the asymmetric C=O stretch bonds at 1710 cm-1 which corresponds to the out-of-plane optical response of the imide I conformation .
Figure 2 shows FTIR spectra of both PAA coatings after the SB at 150 °C and PI films after a HC at 250 °C. Spectra have been normalized to the classical C=C absorption band appearing at 1518 cm-1. The spectrum performed after the SB shows the typical absorption bands of PAA coatings. The large absorption band observed between 2300 and 3400 cm-1 corresponds to the N–H stretch vibration modes, the C–H stretch bonds and the O–H stretch bonds present in both the PAA and NMP solvent. The FTIR spectrum of PI films already shows the typical completion of the imidization reaction with the presence of the four absorption bands from the imide rings. They occur at 1775/1734 cm-1 (imide I), 1371 cm-1 (imide II), 1124/1080 cm-1 (imide III) and 737 cm-1 (imide IV). Moreover, it is possible to observe the large absorption band induced by the C–H stretch vibration modes between 2600 and 3100 cm-1. At 1415 cm-1, a shoulder appears near the C–N stretch peak. This absorption band could be attributed to symmetric stretch of carboxylate ion COO–. The carboxylic acid groups present in PAA appear through the O–H stretching bonds at 3400 cm-1 but free carboxylic acid groups can be deprotonated by the weak amine base . Consequently, COO– carboxylate ions are usually also present in PIs exhibiting two peaks around 1606 and 1415 cm-1. This could explain the release of mobile H+ protons (from COOH) responsible of electrical conduction in PI .
FTIR measurements have been performed for different imidization temperatures
To study the imidization kinetics of PI films, the peak of aromatic ring (C=C) stretching around 1500 cm-1 is chosen as a reference and the peak height method is adopted to calculate the amount of the appearing imide groups formed. The degree of imidization (DOI) is thus defined by comparing the intensity of an imide absorption peak normalized to the intensity of the C=C reference band and is given by :
Figure 3b shows the extent of imidization of the main bonds of BPDA-PDA versus the imidization temperature. Most of the imidization reaction takes place rapidly with a conversion rate as high as 70-85% at 250 °C and still continues slightly up to 400 °C as shown through the increase in the magnitude of the imide bands. However, it is difficult to detect the optimum imidization temperature (i.e. the highest magnitude) to not exceed in order to preserve PI from degradation. For instance at 450 °C, the imide II and IV absorption bands decrease of 20% and 10% respectively showing the initiation of a desimidization of the structure. Therefore, the use of complementary electrical measurements as a probe of the imidization advancement can allow obtaining a higher accuracy regarding the optimal temperature of the curing.
2.2.2. Electrical properties
As for the DOI, the electrical properties strongly depend on the imidization temperature. Changes in the electrical conductivity, dielectric properties or in the dielectric breakdown field of the PI films can be used to determine precisely the optimal imidization temperature. Larger the DOI is, better the electrical properties are expected due to a lower impurities amount in the PI films.
3. Thickness influence on the structural and dielectric properties of BPDA-PDA polyimide
3.1. Influence on the chemical structure
The influence of the thickness of PI films on the chemical structure is rarely investigated. Figure 5 shows FTIR spectra of BPDA-PDA imidized at 400 °C for different film thicknessses. As represented by the downward arrows, one can observe that the quantity and the intensity of the bands corresponding to the amide bonds increase when increasing the film thickness. Hence, for higher film thicknesses, the conversion rate of PAA into PI is strongly affected either due to a bad diffusion of the temperature within the medium of the coating bulk during the curing process (presence of unreacted PAA) or due to a higher difficulty to remove by-products such as solvent and water molecules inherent in the imidization reaction. Unfortunately, this issue cannot be solved by higher temperatures or longer curings because in this range the desimidization of PI starts. Consequently, all these remaining impurities can act as ionizable centers supplying free mobile charges.
3.2. Influence on the electrical properties
Wheras such a phenomenon can be negligeable for low temperature applications (< 150 °C) because of the low mobility of free charges, this can be more influent at high temperature (>200 °C). Figure 6a shows the temperature dependence of the dc conductivity of BPDA-PDA between 200 °C and 350 °C for thicknesses from 1.5 μm up to 20 μm. At 200 °C, the dc conductivity is one order of magnitude higher for the thickest films compared to the one of the thinnest films. In comparison at 300 °C, the dc conductivity is two orders of magnitude higher for the thickest films than for the thinnest ones. The fact that the low field dc conductivity is thickness-dependent, particularly in the high temperature range, is directly related to the presence into BPDA-PDA of unreacted PAA impurities for which temperature supplies sufficient energy to the free charges to become mobile.
Figure 6b shows the temperature dependence of the dielectric strength of BPDA-PDA between 200 °C and 350 °C for thicknesses from 1.5 μm up to 8.6 μm. Same findings can be done in this high electric field region. The larger presence of PAA impurities in the thickest films leads to substantially decrease the dielectric breakdown field of 15% at 200 °C (compared to thinnest films) and of 55% at 350 °C. In these thick films, the earlier breakdown event could be explained by a prematured Joule effect occuring when a higher conduction current magnitude happens across the film during the voltage raising. Thus, the breakdown channel appears for lower applied electric fields.
4. Thermal aging of BPDA-PDA polyimide
The effect of long time aging of polyimide at high temperature (>200 °C) and in oxidative environment on the mechanical properties , weight loss [40,41], and chemical properties [42,43], was widely investigated for thick polyimide matrix composites (1 mm thick) used in high temperature aerospace applications. It was found that while thermal degradation occurred throughout the material, the oxidative degradation occurs mainly within a thin surface layer where oxygen diffuses into the material. Few papers discussed the effect of thermal aging on the electrical properties of PIs and this is always for thick and freestanding films [44,45]. Consequently, an overall understanding of the thermo-oxidative aging mechanisms (for PI thickness <20 μm) and their effects on the electrical properties are still lacking.
All the measurements presented below were performed on PI films deposited on highly doped N++ cleaned silicon wafers (resistivity < 3×10-3 Ω cm) and aged at high temperature. The time at the beginning of the aging is noted as
4.1. Thermal stability of PIs
For PIs, it has been shown that the increase in the number of benzene rings contributes to an increase in the degradation temperature . However, the degradation temperature can be also affected by the presence of low thermo-stable bonds in the macromolecular structure. For instance, even if BPDA-PDA and PMDA-ODA (Kapton-type) own the same number of benzene rings (i.e. three in elementary monomer backbone), the absence of the C—O—C ether group in the case of BPDA-PDA allows increasing
4.2. Thermal aging in inert atmosphere
Figure 8 shows the evolution of the FTIR spectrum of BPDA-PDA before and after an aging at 300 °C in nitrogen during 1000 h and the evolution of the film thickness and the related breakdown field during this aging. One can notice that at this temperature in inert atmosphere, no change in the vibration bonds is remarkable even after a long period of aging. This is in agreement with a good stability of both the film thickness and the high field dielectric properties.
Moreover, a similar observation were done for aging at higher temperature. Indeed, up to
4.3. Thermal aging below
T gin oxidative atmosphere
The aging effects up to 5000 h at 300 °C in air on different properties of BPDA-PDA were measured on three different initial thicknesses varying from 1.5 μm to 8 μm. For comparison, a same aging was performed on BPDA-ODA, with a glass transition
The chemical structure variation was measured by FTIR and the spectra of the 4.2 μm-thick film is presented in Figure 9a. A quasi-stabilisation of almost all the peaks can be revealed during 5000 h specially the imide ones (see Figure 9b). However, an increase in the peak localized at 1212 cm-1 related to the asymmetric vibration of the C-O-C band can be observed. This can indicate the occurrence of additional oxidation of the unreacted polyamic acid, which was not completely imidized during the curing cycle.
On the contrary, for BPDA-ODA films (see Figure 9c and 9d), the same aging at 300 °C during 1000 h shows as soon as the first 200 h a strong decrease in all the main vibration bonds. Consequently, such an aging affects the chemical integrity of the chemical backbone and the physical properties would be modified.
If we look at the film thicknesses, the BPDA-PDA films do not show any thickness variation during 5000 h of aging, indicating that neither densification nor degradation occurred. On the other hand, the BPDA-ODA films loose more than 50% of their initial thickness after 1000 h of aging, reflecting the strong degradation in this case.
The effect of the aging under air atmosphere on the breakdown field and low field dielectric properties measured at the aging temperatures, for the BPDA-PDA and BPDA-ODA films, are now presented and discussed. The breakdown field, performed by polarizing positively the gold electrode, for different initial BPDA-PDA thicknesses and one BPDA-ODA thickness are presented in Figure 11. Whereas a stabilization of the breakdown field during the 5000 h aging is observed for the BPDA-PDA films, a continuous decrease is observed for the BPDA-ODA films. This invariance of the breakdown field of BPDA-PDA is in good agreement with the good stability of FTIR spectra during aging. On the contrary, the strong decrease in the breakdown field of BPDA-ODA after only 1000 h highlights the progressive and fast degradation of the imide bonds in this kind of PIs.
The dielectric constant
4.4. Thermal aging above
T gin oxidative atmosphere
In order to check the stability of BPDA-PDA films at higher temperatures, aging has been performed at different temperatures above
BPDA-PDA films 4.2 μm-thick were aged in air at 360 °C during 800 h. The FTIR spectrum does not show any variation in the imide bonds during this aging period (not shown here) indicating that the bulk of the material is not affected by the aging. Here also, the measured relative permittivity at 1 kHz remains constant with a value of 2.8 during all the aging period (not shown here), indicating that no additional polar groups are formed during the aging. In contrast the film thickness and the breakdown field measured at 300 °C, present a slight continuous decrease during the aging as illustrated in Figure 14. After 800 h a breakdown field decrease of about 50 % while a thickness reduction of 14% can be measured. During this aging, an increase in the surface roughness of BPDA-PDA and the formation of craters were observed (not shown here). They can cause local field intensification and assist the dielectric breakdown mechanism. Such a surface state degradation can explain the breakdown field decrease during the aging. So, it is believed that the observed degradations are related to the oxygen presence since no variation occurs during aging at the same temperature but in inert gas. Thus, BPDA-PDA is attacked at the outer layer face exposed to oxygen.
All these results lead to show that BPDA-PDA is a reliable kind of PIs in order to passivate wide band gap semiconductor devices up to 360 °C during extremely long duration in inert atmosphere without any remarkable properties degradation.
5. Secondary passivation of SiC bipolar diodes with BPDA-PDA polyimide
The secondary passivation is the last fabrication step, at the wafer level, of a semiconductor device. It aims to reinforce the die protection against mechanical aggressions, chemical contamination, and surface electric flashover under blocking voltage operation. Note that after the wafer dicing and die packaging, a complementary insulating environment (moulding case, silicone gel, …), may be required over the device depending on the maximal voltage rating, in order to avoid electrical arcing in air during operation. Coming back at the wafer level, the component secondary passivation fabrication step consists in two main phases: the first one corresponds to the wafer PI coating, the second one corresponds to the PI film etching at the component metal electrode areas, in order to allow ulterior electrical contacting.
The feasibility of using BPDA-PDA polyimide for the passivation of high voltage silicon carbide bipolar diodes has been studied . As BPDA-PDA material is not photosensitive and not removable using wet etching, its local etching requires applying a plasma process through a previously deposited metal mask. The following sections will first present the aimed diode structure and the used BPDA-PDA coating and ectching processes. Then, the component electrical characterizations will be reported. The results of this paragraph are extracted from .
5.1. Diodes fabrication, passivation process and plasma etching
4H-SiC PiN diodes were realized on a 2’’-SiC wafer in a 60 µm-thick N– epilayer (
Then, the second passivation layer has been realized with the spin-coated BPDA-PDA through a multi-layer (3 layers) coating process onto the wafer. In order to reinforce the adhesion with the primary passivation layer, an adhesion promottor (containing silane groups) was first spin-cast onto the wafer at 3000 rpm. A first layer of BPDA-PDA PAA solution was spin-coated at 500 rpm followed by a rotation speed at 3000 rpm. The wafer was consecutively baked at 100 °C for 1 minute and 175 °C for 3 minutes on a hot plate. A second and a third BPDA-PDA PAA layers were coated with the same process in order to increase the passivation layer thickness. The wafer was finally hard cured
Before the etching, a mask metallic layer of 300 nm was evaporated into vacuum onto the BPDA-PDA passivation layer. The metallic layer was opened (metal etch) just above the SiC diode anodes using the photolithography technique. Plasma etching of the unmasked BPDA-PDA areas was performed into a plasma reactor containing a 100% O2 atmosphere at pressure of 1 mTorr. The injected micro-wave electrical power was 600 W. An auto-polarization voltage of -84 V was applied between the plasma electrodes. The incident RF power was 70 W while the reflected power was negligeable (around 3 W). The wafer was placed onto the ground electrode of the reactor which was cooled with water to maintain the temperature of the wafer around 10 °C. The etching was performed during 20 minutes by short steps of 5 minutes long in order to avoid an increase in the temperature of the wafer and until the total removing of exposed BPDA-PDA areas. Figure 15 shows optical and SEM images of the upper electrode of a SiC diode after the plasma etching of BPDA-PDA.
5.2. Electrical characterizations of BPDA-PDA passivated SiC bipolar diodes
The diode forward and reverse current
The typical high voltage reverse characteristics measured at ambient temperature for the selected best diodes are shown on Figure 17a. The breakdown event always occurred suddenly, at a voltage value between 5 kV and 6 kV, and leaving a visible mark on the sample located relatively far from the tested component (at a distance longer than 1 mm) as presented on Figure 17b.
The tested diodes were not destroyed after the first high voltage measurement, exhibiting approximately the same breakdown voltage values when polarized again several times. Considering the reverse voltage values achieved and the distance observed between the resulting crater and the device, the second passivation layer is certainly at the origin of the failure (the PFPE environment being able to withstand around three times higher voltages), due to the presence of local defects. For another diode, probably situated in a better quality area, a maximal breakdown voltage was measured with a value of 7.3 kV, with a I(V) characteristics presenting a current knee before breakdown, as can be seen on Figure 18a. Such a breakdown voltage value is very close to the theoretical maximal value assuming an avalanche breakdown in the SiC tested structure. Such a SiC avalanche mechanism in this particular case was further supported by the observation of the post-breakdown degraded zone, situated at the diode itself, the latter being totally destroyed as exhibited on Figure 18b.
So the feasibility and the potentiality of the BPDA-PDA films for high voltage SiC device secondary passivation could be experimentally demonstrated, positively affecting the current voltage characteristics and allowing high breakdown voltage typical values with a maximum value close to the theoretical limit to be reached. Moreover, a significant improvement in the BPDA-PDA protection efficiency should result from a fabrication entirely performed in clean room conditions and from the use of thicker PI layers.
This chapter deals with polyimide materials (PIs), having in mind the emerging high temperature semiconductor devices currently demanded for high temperature and high power electronics. Among several PIs already well known for their best thermal properties, very good dielectric characteristics, chemical and radiation resistance, and easy processability, this chapter focuses on BPDA-PDA polyimide, evaluating its superiority for semiconductor insulating coating in the temperature range up to 400 °C.
It is shown that the BPDA-PDA’s CTE, which is the closest to the semiconductors (as SiC and GaN) ones, is not the only advantage of this material with regards to the targeted application. In fact, though exhibiting comparable
The presence of impurities (source of free charges) within the PI films playing a major role in the degradation of their dielectric characteristics above 200 °C, the highest degree of imidization has to be looked for, as considered in this chapter. An imidization cure (400 °C-temperature, 1 h-duration) is found optimal for maximizing both the low field resistivity and the dielectric strength, in correlation with FTIR spectrometry analysis. Because of its impact on the intrinsic free charges density as well, the film thickness parameter is also taken into account. Its strong influence on the high temperature dielectric properties is underlined, which can not be solved by a higher temperature or longer curing (leading to desimidization). As an example, at 350 °C, the mean dielectric strength of a 8.6 μm-thick film is measured two fold lower than that of a 1.5 μm-thick layer; however it is remaining as high as 2 MV/cm, so comparable to SiC critical field.
Going up to the application, the chapter finally describes an experiment demonstrating the feasibility of the secondary passivation of 7.8 kV SiC bipolar diodes, using BPDA-PDA. The PI coating and etching processes are detailed, resulting in a 4 μm-thick PI layer. The electrical characterization results arise that the applied final fabrication step positively affected the high temperature forward I(V) curves of the diodes. In reverse bias, the typical breakdown voltage, of around 70% of the theoretical maximum value, could be attributed to the presence of local defects throughout the PI coating. So, such a first experiment already attests the potentiality of BPDA-PDA for high voltage secondary passivation, knowing that one can expect an even higher protection efficiency using clean room elaboration conditions, and thicker PI layers.