Synthesis of a Novel Polyethoxysilsesquiazane and Thermal Conversion into Ternary Silicon Oxynitride Ceramics with Enhanced Thermal Stability

A novel polyethoxysilsesquiazane ([EtOSi(NH)1.5]n, EtOSZ) was synthesized by ammonolysis at −78 °C of ethoxytrichlorosilane (EtOSiCl3), which was isolated by distillation as a reaction product of SiCl4 and EtOH. Attenuated total reflection-infra red (ATR-IR), 13C-, and 29Si-nuclear magnetic resonance (NMR) spectroscopic analyses of the ammonolysis product resulted in the detection of Si–NH–Si linkage and EtO group. The simultaneous thermogravimetric and mass spectrometry analyses of the EtOSZ under helium revealed cleavage of oxygen-carbon bond of the EtO group to evolve ethylene as a main gaseous species formed in-situ, which lead to the formation at 800 °C of quaternary amorphous Si–C–N with an extremely low carbon content (1.1 wt %) when compared to the theoretical EtOSZ (25.1 wt %). Subsequent heat treatment up to 1400 °C in N2 lead to the formation of X-ray amorphous ternary Si–O–N. Further heating to 1600 °C in N2 promoted crystallization and phase partitioning to afford Si2N2O nanocrystallites identified by the XRD and TEM analyses. The thermal stability up to 1400 °C of the amorphous state achieved for the ternary Si-O-N was further studied by chemical composition analysis, as well as X-ray photoelectron spectroscopy (XPS) and 29Si-NMR spectroscopic analyses, and the results were discussed aiming to develop a novel polymeric precursor for ternary amorphous Si–O–N ceramics with an enhanced thermal stability.


Introduction
Silicon oxynitride (Si 2 N 2 O) is a unique crystalline compound in the silica (SiO 2 )-silicon nitride (Si 3 N 4 ) binary system, and Si 2 N 2 O ceramics exhibit attractive properties for its structural application, such as low theoretical density with high hardness and low thermal expansion coefficient [1], low thermal conductivity [2], excellent oxidation resistance up to 1600 • C, and high temperature strength without degradation up to 1400 • C [3]. Moreover, the low dielectric constant and loss of the porous Si 2 N 2 O material [4] is attractive as ceramic insulators.
Crystalline Si 2 N 2 O can be produced through the following routes: (i) high-temperature solid state reaction of Si 3 N 4 with SiO 2 [5]; (ii) nitridation of a mixture of Si and SiO 2 [6]; (iii) carbothermal reduction nitridation by reacting mixtures of carbon and SiO 2 under flowing nitrogen [7,8]; and, (iv) self-propagating high-temperature synthesis [9,10]. Similar to Si 3 N 4 , Si 2 N 2 O decomposes close to the sintering temperature, and generally hot-pressing is required for fabricating fully dense Si 2 N 2 O ceramics [2,11].

Precursor Synthesis
The handling of all the reagents and products in this study was performed under inert atmosphere of pure nitrogen (N 2 ). Polyethoxysilsesquiazane ([EtOSi(NH) 1.5 ] n , EtOSZ) was synthesized via simple 2-steps reaction (Equations (1) and (2)).
(1) Synthesis of ethoxytrichlorosilane (EtOSiCl 3 ) EtOSiCl 3 (1) A 1 L four-neck round-bottom flask equipped with a dropping funnel, a magnetic stirrer, and a septum, was charged with tetrachlorosilane (500 g, 2.94 mol, Wako Pure Chemicals Industry, Osaka, Japan). Through the funnel, ethanol (99.5%, 172 mL, 2.94 mol, Wako Pure Chemicals Industry) was added dropwise at room temperature over 2 h. The mixture was then stirred at room temperature for additional 1 h. After distillation, 316 g of EtOSiCl 3 was obtained at 102 • C/760 mmHg as a colorless liquid. The purity of the distillated EtOSiCl 3 was monitored by gas chromatography (GC) analysis and the EtOSiCl 3 fraction with the purity higher than 95% was collected and used for next reaction.
Gaseous pure ammonia (NH 3 , >99.9%, Sumitomo Seika Chemicals, Osaka, Japan) at a flow rate of 500 mL/min was bubbled into the solution for 1 h through a glass tube. The suspension was stirred at −78 • C for additional 1 h, and then allowed to warm up to room temperature overnight as the excess of NH 3 evaporated. The NH 4 Cl precipitate was then filtered off under N 2 pressure, and was washed with fresh THF under N 2 atmosphere. The filtrate was transferred into a 500 mL round-bottom flask and removed the solvent under vacuum at 40 • C to afford EtOSZ (12.2 g, 0.128 mol) as colorless solid. The yield was 95%.

Pyrolysis and Heat Treatment
The synthesized EtOSZ was placed on an alumina tray and pyrolyzed in a quartz tube furnace under flowing N 2 (200 mL/min) by heating from room temperature up to 800 • C with a heating rate of 5 • C/min, maintaining the temperature at 800 • C for an additional 1 h and finally furnace cooling down to room temperature to give a product as a slightly brown solid.
The pyrolyzed sample was ground to fine powders using a mortar and a pestle. The powdered sample was placed on a BN plate within a BN crucible and was heat-treated in a graphite resistance-heated furnace (Model High Multi 5000, Fujidempa Kogyo, Osaka, Japan) under vacuum from room temperature to 500 • C. Then, N 2 gas was introduced into the furnace at 500 • C and the temperature was increased to 1400, 1600, or 1800 • C, and was held for an additional 1 h. The heating rate was 10 • C /min. The N 2 pressures that were applied in this heat treatment procedure were 196 kPa between 500 • C and 1200 • C, 392 kPa between 1200 and 1600 • C and 980 kPa between 1600 and 1800 • C. After the heat treatment, the sample was cooled down to room temperature in the furnace. 29 Si solid state nuclear magnetic resonance (NMR) spectra for the as-synthesized EtOSZ polymer and its heat-treated powdered materials were acquired using magic angle spinning (MAS), with a rotation frequency of 15 kHz (Model ECA-400, JEOL, Tokyo, Japan) at room temperature. The resonance frequencies for the 13 C-and 29 Si-NMR spectra that were recorded in this study were 100 and for 79.5 MHz, respectively. The chemical shifts of the peak signals in the 13 C-and 29 Si-NMR spectra were quoted relative to the signals of adamantine (29.5 pm) and 3-(trimethylsilyl) propionic acid sodium salt (2 ppm), respectively.

C and
The Attenuated Total Reflection-Infra Red (ATR-IR) spectra were recorded on the as-synthesized and pyrolyzed EtOSZ with a diamond prism under an incidence angle of 45 • (Model Spectrum 100, Perkin Elmer, Waltham, MA, USA).
The thermal behaviors up to 1000 • C were studied by thermogravimetric/differential thermal analysis (TG/DTA) in air or N 2 (Model TG-DTA 6300, Hitachi High Technologies Ltd., Tokyo, Japan), and simultaneous TG-mass spectrometry (MS) analyses (Model STA7200, Hitachi High Technologies Ltd., Tokyo, Japan/Model JMS-Q1500 GC, JEOL, Tokyo, Japan). The measurements were performed under flowing helium (100 mL/min) with a heating rate of 10 • C/min.
Elemental analyses were performed on the pyrolyzed or heat-treated samples for oxygen, nitrogen, and hydrogen (inert-gas fusion method, Model EMGA-930, HORIBA, Ltd., Kyoto, Japan), and carbon (non-dispersive infrared method, Model CS844, LECO Co., St. Joseph, MI, USA). The silicon content in the samples was calculated as the difference of the sum of the measured C, N, O, and H content to 100 wt %.
Crystallization behavior of the EtOSZ-derived amorphous silicon oxynitride (Si-O-N) materials was observed by using a transmission electron microscope (TEM, Model 2010, JEOL, Tokyo, Japan, operating at 200 kV, camera length = 80 cm).

Chemical Structure of EtOSZ
The chemical structure of the synthesized EtOSZ was initially studied by the ATR-IR spectroscopic analysis. As shown in Figure 1, the spectrum of the as-synthesized sample exhibited characteristic absorption bands at 3350 (broad), 2800-3000, and 1070 cm −1 , attributed to νN-H, νC-H, and δN-H that were involved in Si-NH-Si unit [26], respectively. X-ray diffraction (XRD) measurements were performed on pyrolyzed or heat-treated samples (Model X'pert Pro α1, Philips Ltd., Amsterdam, The Netherlands).
Crystallization behavior of the EtOSZ-derived amorphous silicon oxynitride (Si-O-N) materials was observed by using a transmission electron microscope (TEM, Model 2010, JEOL, Tokyo, Japan, operating at 200 kV, camera length = 80 cm).

Chemical Structure of EtOSZ
The chemical structure of the synthesized EtOSZ was initially studied by the ATR-IR spectroscopic analysis. As shown in Figure 1, the spectrum of the as-synthesized sample exhibited characteristic absorption bands at 3350 (broad), 2800-3000, and 1070 cm −1 , attributed to νN-H, νC-H, and δN-H that were involved in Si-NH-Si unit [26], respectively. To identify the chemical structure of the EtOSZ in more details, 13 C-and 29 Si-NMR spectroscopic analyses were performed in solid state. Results were shown in Figure 2. The 13 C-NMR spectrum presented two sharp signals at 58.0 and 18.8 ppm, assigned to methylene (CH2) unit, and terminate methyl (CH3) unit in the ethoxy (OCH2CH3) group, respectively [27]. On the other hand, the corresponding 29 Si-NMR spectrum exhibited a strong single signal at −44.6 ppm that was assigned to SiO(NH)3 unit of the reaction product, EtOSZ ([CH3CH2OSi(NH)1.5]n). The weak signals at −53.6 and −61.4 ppm were thought to be attributed to by-products that could not be removed by the distillation after the alkoxylation of SiCl4 (Equation (1)). The signals at −53.6 and −61.4 ppm were assigned to (EtO)2-Si-(NH)2 (linear or cyclic) and (EtO)3-Si-NH, respectively. As mentioned in the experimental section, the purity of the distilled EtOSiCl3 was higher than 95%, and the total amount of these by-products was small.
These results supported that the two-steps reaction route that was investigated in this study is useful for the synthesis of EtOSZ. To identify the chemical structure of the EtOSZ in more details, 13 C-and 29 Si-NMR spectroscopic analyses were performed in solid state. Results were shown in Figure 2. The 13 C-NMR spectrum presented two sharp signals at 58.0 and 18.8 ppm, assigned to methylene (CH 2 ) unit, and terminate methyl (CH 3 ) unit in the ethoxy (OCH 2 CH 3 ) group, respectively [27]. On the other hand, the corresponding 29 Si-NMR spectrum exhibited a strong single signal at −44.6 ppm that was assigned to SiO(NH) 3 unit of the reaction product, EtOSZ ([CH 3 CH 2 OSi(NH) 1.5 ] n ). The weak signals at −53.6 and −61.4 ppm were thought to be attributed to by-products that could not be removed by the distillation after the alkoxylation of SiCl 4 (Equation (1)). The signals at −53.6 and −61.4 ppm were assigned to (EtO) 2 -Si-(NH) 2 (linear or cyclic) and (EtO) 3 -Si-NH, respectively. As mentioned in the experimental section, the purity of the distilled EtOSiCl 3 was higher than 95%, and the total amount of these by-products was small.
These results supported that the two-steps reaction route that was investigated in this study is useful for the synthesis of EtOSZ. Materials 2017, 10, 1391 5 of 12  29 Si-NMR spectra of EtOSZ.

Conversion to Inorganic Compound
To study the thermal property of the EtOSZ that was synthesized in this study, the TG/DTA analyses both in air and in N2 atmosphere were, respectively, performed. The results are shown in Figure 3. In air (Figure 3a), the sample showed a slight weight loss of approximately 2.5% up to 200 °C, which could be due to the residual solvent. Then, a main weight loss was observed at around 300 to 600 °C, with a distinct exothermic peak that was centered at 321 °C, typical for the combustion of organic molecules. The final recovery rate (ceramic yield) at 1000 °C was 60%. This yield was assumed to be recognized as a result of the combustion of organic substituents and subsequent oxidation of Si atom in the EtOSZ to yield silica (Equation (3)), since the observed mass loss was consistent with the weight difference between the molecular unit of EtOSZ (CH3CH2OSi(NH)1.5) and the molecular weight of silica (SiO2).
Under flowing N2 (Figure 3b), EtOSZ also showed a main weight loss at the same temperatures ranging from 300 to 600 °C, and the ceramic yield at 1000 °C was 58%, close to that achieved in air, while a weak and very broad exothermic peak appeared at 50 to 700 °C.
In the ATR-IR spectrum for the sample after pyrolysis at 800 °C in N2 (Figure 1), the characteristic peaks due to the organic substituents disappeared and the spectrum was similar to that of silica composed of a weak and broad band at 3000-3700 cm −1 and a strong band centered around 1010 cm −1 assigned to intermolecular hydrogen-bonded Si-OH groups and νas Si-O in Si-O-Si linkage [27,28].
To study the chemical structure of the 800 °C-pyrolyzed EtOSZ in more detail, 29 Si-NMR spectroscopic analysis was performed. The result was shown in Figure 4.  29 Si-NMR spectra of EtOSZ.

Conversion to Inorganic Compound
To study the thermal property of the EtOSZ that was synthesized in this study, the TG/DTA analyses both in air and in N 2 atmosphere were, respectively, performed. The results are shown in Figure 3.  29 Si-NMR spectra of EtOSZ.

Conversion to Inorganic Compound
To study the thermal property of the EtOSZ that was synthesized in this study, the TG/DTA analyses both in air and in N2 atmosphere were, respectively, performed. The results are shown in Figure 3. In air (Figure 3a), the sample showed a slight weight loss of approximately 2.5% up to 200 °C, which could be due to the residual solvent. Then, a main weight loss was observed at around 300 to 600 °C, with a distinct exothermic peak that was centered at 321 °C, typical for the combustion of organic molecules. The final recovery rate (ceramic yield) at 1000 °C was 60%. This yield was assumed to be recognized as a result of the combustion of organic substituents and subsequent oxidation of Si atom in the EtOSZ to yield silica (Equation (3)), since the observed mass loss was consistent with the weight difference between the molecular unit of EtOSZ (CH3CH2OSi(NH)1.5) and the molecular weight of silica (SiO2).
Under flowing N2 (Figure 3b), EtOSZ also showed a main weight loss at the same temperatures ranging from 300 to 600 °C, and the ceramic yield at 1000 °C was 58%, close to that achieved in air, while a weak and very broad exothermic peak appeared at 50 to 700 °C.
In the ATR-IR spectrum for the sample after pyrolysis at 800 °C in N2 (Figure 1), the characteristic peaks due to the organic substituents disappeared and the spectrum was similar to that of silica composed of a weak and broad band at 3000-3700 cm −1 and a strong band centered around 1010 cm −1 assigned to intermolecular hydrogen-bonded Si-OH groups and νas Si-O in Si-O-Si linkage [27,28].
To study the chemical structure of the 800 °C-pyrolyzed EtOSZ in more detail, 29 Si-NMR spectroscopic analysis was performed. The result was shown in Figure 4. In air (Figure 3a), the sample showed a slight weight loss of approximately 2.5% up to 200 • C, which could be due to the residual solvent. Then, a main weight loss was observed at around 300 to 600 • C, with a distinct exothermic peak that was centered at 321 • C, typical for the combustion of organic molecules. The final recovery rate (ceramic yield) at 1000 • C was 60%. This yield was assumed to be recognized as a result of the combustion of organic substituents and subsequent oxidation of Si atom in the EtOSZ to yield silica (Equation (3)), since the observed mass loss was consistent with the weight difference between the molecular unit of EtOSZ (CH 3 CH 2 OSi(NH) 1.5 ) and the molecular weight of silica (SiO 2 ).
Under flowing N 2 (Figure 3b), EtOSZ also showed a main weight loss at the same temperatures ranging from 300 to 600 • C, and the ceramic yield at 1000 • C was 58%, close to that achieved in air, while a weak and very broad exothermic peak appeared at 50 to 700 • C.
In the ATR-IR spectrum for the sample after pyrolysis at 800 • C in N 2 (Figure 1), the characteristic peaks due to the organic substituents disappeared and the spectrum was similar to that of silica composed of a weak and broad band at 3000-3700 cm −1 and a strong band centered around 1010 cm −1 assigned to intermolecular hydrogen-bonded Si-OH groups and ν as Si-O in Si-O-Si linkage [27,28].
Chemical composition of the 800 °C-pyrolyzed EtOSZ was listed in Table 1. As a reference data, the theoretical composition of the as-synthesized EtOSZ was also listed in this table. In spite of the pyrolysis under inert atmosphere of N2, the carbon content remarkably decreased from 25.1 to 1.1 wt %, and the resulting C/Si atomic ratio was 0.05. The N/Si atomic ratio also decreased from 1.5 to 0.5, while the O/Si atomic ratio was 1.1, and close to that of the ideal EtOSZ (1.0). Then, TG-MS analysis was performed on the as-synthesized EtOSZ under He atmosphere. The results were summarized and are shown in Figure 5.  One broad peak at around −100 ppm was deconvoluted to three broad peaks centered at −110, −100, and −90 ppm that were assigned to silicon tetrahedral units of SiO 4 [29], HO-SiO 3 (Q3) [30], and SiO 3 N [31,32], respectively.
Chemical composition of the 800 • C-pyrolyzed EtOSZ was listed in Table 1. As a reference data, the theoretical composition of the as-synthesized EtOSZ was also listed in this table. In spite of the pyrolysis under inert atmosphere of N 2 , the carbon content remarkably decreased from 25.1 to 1.1 wt %, and the resulting C/Si atomic ratio was 0.05. The N/Si atomic ratio also decreased from 1.5 to 0.5, while the O/Si atomic ratio was 1.1, and close to that of the ideal EtOSZ (1.0). Then, TG-MS analysis was performed on the as-synthesized EtOSZ under He atmosphere. The results were summarized and are shown in Figure 5.
The TG-curve that was measured in He was quite similar to the previous one in N 2 (Figure 3b), and the gaseous species formed in-situ were mainly detected during the main weight loss at 300 to 600 • C. As-shown in Figure 5a, the total ion current chromatogram (TICC) spectrum showed a broad bimodal signal composed of a weak peak at 300 to 400 • C, and a dominant one at 400 to 600 • C. The simultaneous MS analysis resulted in the detection of three kinds of gaseous species at the m/z ratios of 45, 28, and 16 ( Figure 5b).
In spite of the pyrolysis under inert atmosphere of N2, the carbon content remarkably decreased from 25.1 to 1.1 wt %, and the resulting C/Si atomic ratio was 0.05. The N/Si atomic ratio also decreased from 1.5 to 0.5, while the O/Si atomic ratio was 1.1, and close to that of the ideal EtOSZ (1.0). Then, TG-MS analysis was performed on the as-synthesized EtOSZ under He atmosphere. The results were summarized and are shown in Figure 5.  The gaseous species, m/z ratios at 45 and 16 were assigned to SiNH 3 + and NH 2 + , respectively.
These fragment ions could be due to the partial decomposition of the silsesquiazane linkage, which leading to the lower nitrogen content observed for the 800 • C-pyrolysed sample. On the other hand, the m/z ratio at 28 could be assigned to ethylene (CH 2 = CH 2 + ), and it turned out that the dominant thermal decomposition reaction of the EtOSZ was the C-O bond cleavage of the ethoxy group to afford CH 2 = CH 2 + as the main hydrocarbon gaseous product (Equation (4)), which was leading to the remarkable decrease in carbon content: -Si-O-CH 2 -CH 3 → -SiO + + CH 2 = CH 2 + + 1/2H 2 (4)

Crystallization Behavior of EtOSZ-Derived Amorphous Si-O-N in N 2
Polymer-derived ternary and quaternary amorphous Si-(M)-C-N (M = B, Ti, etc.) show a unique high-temperature stability in terms of restricting crystallization and subsequent phase partitioning under an inert atmosphere of N 2 or Ar [20,21]. On the other hand, very limited study has been done for the crystallization behavior of polymer-derived ternary Si-O-N or quaternary Si-O-C-N systems [22,24]. Therefore, high-temperature crystallization behavior above 1000 • C of the present EtOSZ-derived amorphous Si-O-C-N was further studied. To restrict Si-N bond cleavage, as mentioned in the experimental section, the additional heat treatment at 1200 to 1400 • C, and above 1400 • C, were performed under the N 2 atmospheres of 392 and 980 kPa, respectively. As shown in Figure 6, the total weight loss up to 1800 • C of the 800 • C-pyrolyzed sample was approximately 9%, and was found to be much lower than that during pyrolysis up to 800 • C (42 %, Figure 3b). The TG-curve that was measured in He was quite similar to the previous one in N2 (Figure 3b), and the gaseous species formed in-situ were mainly detected during the main weight loss at 300 to 600 °C. As-shown in Figure 5a, the total ion current chromatogram (TICC) spectrum showed a broad bimodal signal composed of a weak peak at 300 to 400 °C, and a dominant one at 400 to 600 °C. The simultaneous MS analysis resulted in the detection of three kinds of gaseous species at the m/z ratios of 45, 28, and 16 ( Figure 5b).
The gaseous species, m/z ratios at 45 and 16 were assigned to SiNH3 + and NH2 + , respectively. These fragment ions could be due to the partial decomposition of the silsesquiazane linkage, which leading to the lower nitrogen content observed for the 800 °C-pyrolysed sample. On the other hand, the m/z ratio at 28 could be assigned to ethylene (CH2 = CH2 + ), and it turned out that the dominant thermal decomposition reaction of the EtOSZ was the C-O bond cleavage of the ethoxy group to afford CH2 = CH2 + as the main hydrocarbon gaseous product (Equation (4)), which was leading to the remarkable decrease in carbon content:

Crystallization Behavior of EtOSZ-Derived Amorphous Si-O-N in N2
Polymer-derived ternary and quaternary amorphous Si-(M)-C-N (M = B, Ti, etc.) show a unique high-temperature stability in terms of restricting crystallization and subsequent phase partitioning under an inert atmosphere of N2 or Ar [20,21]. On the other hand, very limited study has been done for the crystallization behavior of polymer-derived ternary Si-O-N or quaternary Si-O-C-N systems [22,24]. Therefore, high-temperature crystallization behavior above 1000 °C of the present EtOSZ-derived amorphous Si-O-C-N was further studied. To restrict Si-N bond cleavage, as mentioned in the experimental section, the additional heat treatment at 1200 to 1400 °C, and above 1400 °C, were performed under the N2 atmospheres of 392 and 980 kPa, respectively. As shown in Figure 6, the total weight loss up to 1800 °C of the 800 °C-pyrolyzed sample was approximately 9%, and was found to be much lower than that during pyrolysis up to 800 °C (42 %, Figure 3b). To study the composition change during the heat treatment up to 1800 °C, elemental analyses were performed on the heat-treated samples. The results were summarized in Table 1. Since the carbon and hydrogen contents in the heat-treated samples were negligibly small (below 0.5%), the compositions of the samples were also plotted in the ternary Si-O-N phase diagram (Figure 7). As a reference sample, 800 °C-pyrolyzed sample was also plotted in this diagram without counting the To study the composition change during the heat treatment up to 1800 • C, elemental analyses were performed on the heat-treated samples. The results were summarized in Table 1. Since the carbon and hydrogen contents in the heat-treated samples were negligibly small (below 0.5%), the compositions of the samples were also plotted in the ternary Si-O-N phase diagram (Figure 7). As a reference sample, 800 • C-pyrolyzed sample was also plotted in this diagram without counting the contents of carbon and hydrogen. Upon heating to 1400 • C, carbon in the EtOSZ-derived Si-O-C-N could be almost spent out to yield gaseous CO x (x = 1, 2). The resulting composition of the 1400 • C-heated sample that was located close to the tie line between Si 2 N 2 O and SiO 2 . Then, above 1400 • C, the position shifted toward SiO 2 along the Si 2 N 2 O-SiO 2 tie line due to the decreasing nitrogen content.   [33]. This value was closed to that reported for amorphous silicon oxynitride (102.4 eV) [34] and was consistent with the random bonding model for the partial replacement of oxygen in the SiO4 tetrahedron by nitrogen, causing the lower binding energies of the Si2p binding energy [35].
After the heat treatment at 1600 °C, the Si2p binding energy was centered at 103 eV (Figure 8a). By the 1600 °C-heat treatment, the peak center of the N1s binding energy also shifted from 397.8 to 398.2 eV (Figure 8c). These peaks that shift behaviors toward higher binding energy were consistent with the decrease in nitrogen content (Table 1, Figure 7), as reported for the ternary amorphous silicon oxynitride (Si-O-N) by Weeren et al. [32]. The peak centers of the O1s binding energies for the 1400 °C-and 1600 °C-heated samples were 532.2 and 532.7 eV, respectively (Figure 8b). These values were also compatible with those reported for SiO2 and amorphous silicon oxynitride having nitrogen content ranging from 0 to 47 at %.
These results indicate that the EtOSZ that was investigated in this study could be converted to a unique oxygen rich amorphous silicon oxynitride (Si-O-N) by pyrolysis at 800 °C, followed by heat treatment at 1400 °C in N2.   [33]. This value was closed to that reported for amorphous silicon oxynitride (102.4 eV) [34] and was consistent with the random bonding model for the partial replacement of oxygen in the SiO 4 tetrahedron by nitrogen, causing the lower binding energies of the Si2p binding energy [35].
After the heat treatment at 1600 • C, the Si2p binding energy was centered at 103 eV ( Figure 8a). By the 1600 • C-heat treatment, the peak center of the N1s binding energy also shifted from 397.8 to 398.2 eV (Figure 8c). These peaks that shift behaviors toward higher binding energy were consistent with the decrease in nitrogen content (Table 1, Figure 7), as reported for the ternary amorphous silicon oxynitride (Si-O-N) by Weeren et al. [32]. The peak centers of the O1s binding energies for the 1400 • Cand 1600 • C-heated samples were 532.2 and 532.7 eV, respectively (Figure 8b). These values were also compatible with those reported for SiO 2 and amorphous silicon oxynitride having nitrogen content ranging from 0 to 47 at %.
These results indicate that the EtOSZ that was investigated in this study could be converted to a unique oxygen rich amorphous silicon oxynitride (Si-O-N) by pyrolysis at 800 • C, followed by heat treatment at 1400 • C in N 2 .
As shown in Figure 9, this material was found to keep X-ray amorphous up to 1400 • C. Then, after the 1600 • C-heat treatment, the sample began to show a diffraction pattern that was identical to crystalline Si 2 N 2 O (JCPDS 47-1627) [36], and the intensity of the Si 2 N 2 O diffraction peaks increased to some extent by the 1800 • C-heat treatment. Actually, as shown in Figure 10a, the 1400 • C-heated sample exhibited a futureless structure, which is typical for amorphous compounds. Then, after the 1600 • C-heat treatment, some crystallites of several ten nanometers in size were observed within the amorphous matrix (marked by arrows in Figure 10b). The inter planer spacing that was observed for the nanocrystallite formed in-situ was measured to be 0.336 nm, which was corresponding to (111) plane of orthorhombic Si 2 N 2 O [36] (Figure 10c), and the selected area electron diffraction (SAED) pattern that was obtained from the nanocrystallite could be also indexed as (110) orthorhombic Si 2 N 2 O [36] (Figure 10d).
with the decrease in nitrogen content (Table 1, Figure 7), as reported for the ternary amorphous silicon oxynitride (Si-O-N) by Weeren et al. [32]. The peak centers of the O1s binding energies for the 1400 °C-and 1600 °C-heated samples were 532.2 and 532.7 eV, respectively (Figure 8b). These values were also compatible with those reported for SiO2 and amorphous silicon oxynitride having nitrogen content ranging from 0 to 47 at %.
These results indicate that the EtOSZ that was investigated in this study could be converted to a unique oxygen rich amorphous silicon oxynitride (Si-O-N) by pyrolysis at 800 °C, followed by heat treatment at 1400 °C in N2.  As shown in Figure 9, this material was found to keep X-ray amorphous up to 1400 °C. Then, after the 1600 °C-heat treatment, the sample began to show a diffraction pattern that was identical to crystalline Si2N2O (JCPDS 47-1627) [36], and the intensity of the Si2N2O diffraction peaks increased to some extent by the 1800 °C-heat treatment. Actually, as shown in Figure 10a, the 1400 °C-heated sample exhibited a futureless structure, which is typical for amorphous compounds. Then, after the 1600 °C-heat treatment, some crystallites of several ten nanometers in size were observed within the amorphous matrix (marked by arrows in Figure 10b). The inter planer spacing that was observed for the nanocrystallite formed in-situ was measured to be 0.336 nm, which was corresponding to (111) plane of orthorhombic Si2N2O [36] (Figure 10c), and the selected area electron diffraction (SAED) pattern that was obtained from the nanocrystallite could be also indexed as (110) orthorhombic Si2N2O [36] (Figure 10d). To study the unique thermal stability up to 1400 °C of the EtOSZ-derived oxygen-rich amorphous Si-O-N, 29 Si-NMR spectroscopic analysis was performed on the heat-treated samples. The resulting spectra were shown in Figure 4. The 1400 °C-heated sample showed a broad line without peaks that were characteristic for the short-range ordering of tetrahedral Si coordination, such as SiO4, HO-SiO3, and SiO3N. Then, after the 1600 °C-heating, the sample exhibited a relatively strong peak at −63 ppm that was attributed to SiON3 unit [31,32], which composing crystalline Si2N2O along with three broad peaks at around −110, −90 and −74 ppm assigned to SiO4, SiO3N, and SiO2N2 [31,32], respectively. Finally, after the 1800 °C-heating, the spectrum tuned to be composed of a distinct peak of SiON3 unit at −63 ppm and a broad peak centered at -110 ppm assigned to SiO4 unit, which was indicating that the Si2N2O and SiO2 two-phase partitioning was almost completed. To study the unique thermal stability up to 1400 • C of the EtOSZ-derived oxygen-rich amorphous Si-O-N, 29 Si-NMR spectroscopic analysis was performed on the heat-treated samples. The resulting spectra were shown in Figure 4. The 1400 • C-heated sample showed a broad line without peaks that were characteristic for the short-range ordering of tetrahedral Si coordination, such as SiO 4 , HO-SiO 3 , and SiO 3 N. Then, after the 1600 • C-heating, the sample exhibited a relatively strong peak at −63 ppm that was attributed to SiON 3 unit [31,32], which composing crystalline Si 2 N 2 O along with three broad peaks at around −110, −90 and −74 ppm assigned to SiO 4 , SiO 3 N, and SiO 2 N 2 [31,32], respectively. Finally, after the 1800 • C-heating, the spectrum tuned to be composed of a distinct peak of SiON 3 unit at −63 ppm and a broad peak centered at -110 ppm assigned to SiO 4 unit, which was indicating that the Si 2 N 2 O and SiO 2 two-phase partitioning was almost completed. The 800 • C-pyrolysis of EtOSZ resulted in the formation of an inorganic amorphous network that was mainly composed of SiO 4 and HO-SiO 3 units. Moreover, the subsequent heat treatment in N 2 lead to the structural rearrangement to afford random network prior to the formations of SiON 3 and SiO 2 units that are essential for the nucleation and crystallization of thermodynamically stable Si 2 N 2 O and SiO 2 , respectively. As a result, the EtOSZ-derived oxygen rich Si-O-N could keep amorphous state up to 1400 • C in N 2 .

Summary
In this study, a novel preceramic polymer, polyethoxysilsesquiazane (EtOSZ), was designed and synthesized for ternary Si-O-N ceramic system. Chemical structure and the thermal behavior up to 1600 °C in N2 of the synthesized EtOSZ was investigated. The results can be summarized as follows: (1) ATR-IR, 13 C-and 29 Si-NMR spectroscopic analyses revealed that the synthesized polymer was composed of EtOSi(NH)3 unit, and polyethoxysilsesquiazane was successfully synthesized in a good yield via simple two-steps reaction, stoichiometric reaction of SiCl4 with EtOH to afford EtOSiCl3, followed by ammonolysis at −78 °C. (2) Under an inert atmosphere, thermal decomposition of EtOSZ mainly proceeded at around 200

Summary
In this study, a novel preceramic polymer, polyethoxysilsesquiazane (EtOSZ), was designed and synthesized for ternary Si-O-N ceramic system. Chemical structure and the thermal behavior up to 1600 • C in N 2 of the synthesized EtOSZ was investigated. The results can be summarized as follows: (1) ATR-IR, 13 C-and 29 Si-NMR spectroscopic analyses revealed that the synthesized polymer was composed of EtOSi(NH) 3 unit, and polyethoxysilsesquiazane was successfully synthesized in a good yield via simple two-steps reaction, stoichiometric reaction of SiCl 4 with EtOH to afford EtOSiCl 3 , followed by ammonolysis at −78 • C. (2) Under an inert atmosphere, thermal decomposition of EtOSZ mainly proceeded at around 200 to 600 • C, and the resulting ceramic yield after heating to 1000 • C was 58%. (3) The simultaneous TG-MS analyses for the thermal decomposition identified ethylene as a main gaseous species that was formed in-situ, and it was clarified that cleavage of oxygen-carbon bond of the EtO group in the EtOSZ contributed to the formation of the quaternary amorphous Si-O-C-N with extremely low carbon content (1.1 wt %) after pyrolysis at 800 • C in N 2 . (4) Additional heat treatment up to 1400 • C of the 800 • C-pyrolyzed EtOSZ resulted in the further reduction of the carbon content to afford oxygen rich Si-O-N amorphous ceramics. (5) The EtOSZ-derived Si-O-N was found to keep an amorphous state up to 1400 • C in N 2 , then Si 2 N 2 O crystallization started during heat treatment from 1400 to 1600 • C.
The enhanced thermal stability that was achieved for the EtOSZ-derived amorphous Si-O-N in this study could be due to the following structural changes in a short range order: Formation of amorphous network mainly composed of SiO 4 and HO-SiO 3 units at 800 • C, followed by structural rearrangement to afford random amorphous network at around 1400 • C prior to the formation of SiON 3 and SiO 4 units that are essential for the formation of Si 2 N 2 O nanocylstallites-dispersed amorphous SiO 2 composite.