TWI240967B - Plasma surface passivation modification treatment method of low dielectric constant film - Google Patents

Abstract

A plasma surface passivation modification treatment method of low dielectric constant film is to perform surface passivation modification treatment on a siloxane low dielectric constant (low k) film, which comprises placing the film sample into a reaction chamber; introducing N2/H2 mixture gas which is used to generate the ionized plasma by a radio frequency supplier; using the N2/H2 mixture plasma to perform surface passivation modification treatment on the low k film sample; and thus forming Si-C-N and Si-N mixed bonding passivation layer after the optimized modification treatment. The surface passivation layer can prevent impact damage on the low polarization chemical bonding (methyl, Si-H) and dielectric constant (and insulation property) from the subsequent high oxidation or reduction plasma (such as O2 and H2) processes (and annealing treatment) and thus effectiveness of protecting and reinforcing the low k film can be achieved. The passivation layer can be further used as a diffusion barrier layer to alleviate the thermal diffusion of copper towards the low k film, which can avoid using dielectric material with high dielectric behavior or metal diffusion barrier material with high resistivity as the use of such material can increase the total RC delay time of the interconnect in the semiconductor device and decrease the efficiency of device calculations.

Description

1240967 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a plasma surface passivation modification method for a low dielectric constant film, in particular to a Nk mixed plasma surface passivation modification for a low-k film surface. Treatment method: Place the low-k film substrate coated and cured on the surface in the reaction chamber of vacuum glow discharge, and evacuate to less than l (T2-l0-4 Pa, then introduce N2 / H2 The mixed gas (pressure is between 10—1 (pl and RF plasma generator is used to generate plasma; low-k film is treated with this Nz / H2 mixed plasma to form Si-CN and Si-N on the film surface) Contains a nitride purification layer. The presence of this passivation layer can prevent the dielectric constant and leakage current of low-k films from being reduced in other plasma environments (such as 02, H2, N2, etc.) to achieve protection and Strengthen the function of low-k thin film, and also provide a low-diffusion layer between copper and copper thin film. [Previous technology] In order to improve the performance of components, many new materials have been introduced into the integrated circuit chip component manufacturing process ... but due to the nature difference between materials Difficulties in process integration have led to many problems. Among them, in order to reduce the resistance_capacitance (μ) delay of interconnecting wires (plus), Inter-metal Dielectrics are expected to gradually be changed from Si 〇2 (k-4. 2) Transfer to materials with a k value lower than 3. However, since the thermal stability, mechanical strength, and bond stability of low-k materials are lower than si〇2, the oxygen plasma removes light. Resistance, chemical mechanical polishing (CMp), or annealing treatments often lead to the destruction of low-polarity bonds such as aromatic hydroxyl or alkyl groups of low-k materials, degradation of dielectric properties, and reduction of thermal stability. These degradation behaviors It is a serious obstacle to the integration of low-k materials and copper conductors in the Damascene process, and it also causes low-level materials to not be fully integrated into the 1C process as expected. 5 1240967 The dielectric cover currently used in low-k / copper processes The material of the Capping Layer is CVD-SiN or CVD-Sic⑻, whose k value is between ㈤; the conductive cover layer materials include chemical, μ, etc. 'The resistivity is usually higher than 100 μΩ-cm. These cover layers can provide diffusion Obstruction, adhesion promotion and polishing And other functions; however, their high k or high resistivity will increase the overall RC delay time of the interconnecting wires, thus also reducing the performance of the component. Therefore, as the feature size of integrated circuits drops below -100 nanometers, The use of plasma surface passivation and low passivation materials for the development, on-site, and production of ultra-thin coatings is a very critical green question. In recent years, it has been widely studied. Most of these studies have been used. A single reactive gas (or mixed with pure gas) generates electricity, including: W2, N2O, N2, H2 (He), 02 for surface passivation treatment, or using methyl group (CH3) ^^ ria ( Hexamethyldisilazane ^ 1 # HMDS; Trimethyl ^ (TMCS for short) responds to the damaged material (ReeQveiT). However, 'the use of mono-reactive gas will cause the following problems: ⑴ Guxi: Due to the heterogeneous and toxic nature of the excitation, special consideration must be given to machine maintenance, personnel operation, waste discharge, etc., which will greatly cause Costs and maintenance issues; (2) Thermal pre-differentiation (lllennal): Age has three covalent bonds (plus * β_), so higher electric excitation power or higher base must be applied Material processing temperature, which means that the thermal budget is smaller than that in Caike County. The material is fine === __ 于某 —the material is not suitable for ',', and is widely used in various low-k materials. And the process window is often relatively narrow 6 1240967 Therefore 'development can overcome the above-mentioned lack of surface passivation _ production series has become a goal of active efforts The invention is fibrous «surface modification process, this kind of gentle "Environmental friendliness" has a good compatibility with the microelectronics process. Recently, the fluorine gas atmosphere is the most common of Weiji's dielectric materials. However, it is based on environmental protection and the increasing age limit and increasing operating costs. Species of _ gas Gradually replaced by other atmospheres, among which N2, H2, 1 ^ / ¾ have all been used, and the team / jj2 has the most potential. [卜 幻 There is an item in the existing single-atmosphere plasma passivation. One or more of the aforementioned defects, the inventor of this case is to solve the industry with the record and-the rural year is very good __ county research and development test, actively research pills different from the single-plasma treatment (to avoid the above-mentioned defects) to solve the industry I want to overcome the problem of degradation of low-k material properties. After continuous trials and experiments, I finally found that the mixed plasma has the effect of forming surface sulfur, which can age the hybrid

Siloxane Polymer, HOSP) low-k film (k = 2.5) electrical properties. [Summary of the Invention] Before explaining the present invention in detail, first use three examples to highlight three common single-xin gases (〇2, Η2, and Ν2) vacuum glow discharge (Gl0w-discharge) electric music: treatment of stone Effect of low-k film based on oxygen-fired base: _ Case 1: Oxygen plasma treatment _ Oxygen plasma treatment will cause Si-CH3 and Si-ΗC-Η bond break of siloxane low-k film to form Si Dangling Bonds. These dangling bonds can be easily combined with the oxygen atoms in other si-〇 bonds to form a Si-0 network structure. Therefore, 〇2 plasma treatment of dream oxygen burns The cage-like Si-0 of the base film is reduced, and the network-like Si-〇 is increased. The low-polarity bonding of Si-CH3, Si-H and CH is also greatly reduced. The Shixi oxygen-shocked film will cause the loss of low-k characteristics and the significant degradation of insulation and physical properties due to the breakage of its characteristic bonds. Case 2: Hydrogen plasma treatment of cage-shaped Si—0, & one arc, C—H bond in Shixi oxygen-fired low-k film after hydrogen electricity treatment, its low-k characteristics, electricity The degradation of the insulation and physical properties is similar to the treatment of oxygen equipment. This, ·· 〇 will show that tfH2 electricity 4 will cause the breakage of Η and c- 般 as a result of 〇2 electropolymerization. Linji stomach then cross-links with other gadolinium (c 臓 —push-on) to synthesize the Si-0 network structure, which causes the characteristics of Shixi oxygen-based low-k film to decline. _ Case 3: Nitrogen plasma treatment Nitrogen plasma treatment only caused a slight decrease in the M. peak intensity of the Wei-based low-k film, while the network and cage Si-G peak intensity had little change. This result suggests that & amp Lai only causes a few Si—CH3 bond breaks, but it is not easy to promote the transition between cage-like and network Si—0 bond junctions. However, these bond changes will still negatively affect the electrical properties of low-k films. In view of this, the present invention uses ionization generated by a mixed gas (N2 / H2) that is different from the above three single atmosphere examples to perform ion nitridation (ι〇η surface modification. Table · 1 is The present invention is compared with the conventional single-reactive gas (h2, N2, N20, and legs) passivation plasma process characteristics of low-k dielectric materials. Among them, the currently used single reactive gas plasma is in the process of Under consideration, different process bottlenecks will be encountered, but the team / 112 mixed gas and plasma method proposed in the present invention can effectively overcome these process limitations, so it is more suitable for the surface passivation of low-grade materials. The advantages of the ^ / ¾ mixed plasma listed in 1 are further explained as follows: 1. The addition of low-heat pre-isolated H2 can greatly improve the team's free efficiency. Therefore, compared to the 仏 passivation plasma 8 1240967 treatment, ΝνΗ2 mixed Plasma has a lower thermal budget (for this reason, traditional steel plasma nitriding surface hardening treatment does not use Qin Plasma, but instead uses Qin / Guan mixed plasma); 2. 冋 safety-due to the absence of redundant / H2 Corrosive and non-toxic properties NH3 is easy to handle and safer in application; 3. The same clothing and private integration. One is to replace the fluorocarbon etching gas with one of the most courageous plasma atmospheres, and the N2 / H2 gas source is commonly used in the industry, so Has excellent process integration; 4. Low operating costs, Q2, no shortage of H2 resources, and mild physical properties, no cost concerns about subsequent processing 'The use costs are relatively low; 5. Wide process window Yiqin / output allows independent control仏 and π, the pressure of the gas, so it can control the concentration of species containing nitrogen and hydrogen in different proportions, and the process optimization can be adjusted according to the essential characteristics of low-k materials. Table 1 Low-k materials passivation plasma atmosphere Comparison of related process characteristics

In this creative case, it was found that the proper adjustment of the gas ratio, the excitation power of electropolymerization, and the processing time of electrical propagation can make the siloxy low-k film have a good passivation effect to achieve the purpose of strengthening the dielectric properties. 1240967 Wei Zhen can have a deeper-level understanding and understanding of the methods and features of the present invention, and hereby attach a conventional example to explain it in detail as follows. [Embodiment] After spin-coated low-k material (ie, H0SP) is applied on the surface of the substrate of Shixi wafer, it is successively applied at 15 (TC, 20 (TC and 30 (TC each) in a nitrogen gas atmosphere). Bake for a few minutes to remove the gel film, and then place it in a tube oven towel (< 400C) for a one-hour curing process. This low-k film test piece is immediately placed in the atmosphere and pumped to a low temperature. On the base of a vacuum cavity of 10 3 pa (about τ〇ΓΓ), a 13.56 MHz RF power supply is connected to the base of the cavity to generate a plasma, and the plasma atmosphere is 302 Η, Η2, N2 single gas and various 仏 / 112 mixed gases, and use the mass flow controller to adjust its flow size and ratio. All plasma treatments are operated at RF power of 50 to 25 watts. The processed HOSP low-k films are analyzed by Fourier transform infrared spectroscopy (FTIR) for the intensity changes of the main knot junction peaks, especially Si-CH3 (127〇cnfl), and reticulated Si—〇 (104) cm.

—I V) and cage-shaped Si-〇 (1130 cm-1) stretching oscillatory waves in order to identify these plasma treatments for thin-film bonds. ~ F 'through the metal-insulation-semiconductor (Me ^ ai-insuiat〇r-gemic ON (juct〇r, · MIS) capacitance-voltage (c_v) and current-voltage (丨 -v) The measurement can be used to know the influence of plasma treatment on the dielectric constant and insulation of low-k materials. In addition, the X-ray near-edge structure energy spectrum of HOSP was performed by the same source Koda light source. Analysis, Khan estimates the surface bonding transformation caused by electrical processing to HOSP film; the secondary ion mass spectrometry depth profile (SIMS-depth Profile) is used to analyze copper in various "si / HOSP / Cu" heat treatment (300 C, 1 Hours) The diffusion behavior of the test piece can be used to evaluate the diffusive barrier properties of copper to the copper oxide film treated with 〇2, H2, hafnium, and cymbal claw. 1240967 Picture-(a) Just cured ) Η "(c) FTIR spectra of H0sp low-k films after plasma treatment with 〇2 and ⑷N2; these treatments are all 100w / 9 minutes, and all of the pictures include reticulated Si-〇 Three major bond peaks with cage-like si-〇 and si-arc, and two weaker Si_H (2240 cm-1) and ch (2970 cnfl) The comparison of the spectrum (a) with that of the peak position and intensity of the network-shaped and cage-shaped Si—0 bonds of the h0sp low-k film after H2 plasma treatment shows that the Si- The bonding strength of CH3 and Si-H is also significantly reduced. These results show that the H0SP low-k film will suffer considerable damage from the H3H2 plasma, and ⑶ and Hsp with a torsional plasma treatment show similar bond transition patterns. These results are shown in (b) and (c) of Figure 1, respectively. This result shows that the H2 plasma has a similar destructive effect as the 02 plasma, which can lead to the breakage of H to form Si suspension bonds. These Si The dangling bond will form another Si-〇 network structure with other ^ _0, so the cage Si-O of H0SP film after H 2 plasma treatment is reduced, and the network Si-〇 is increased; (A) and (d) It was learned that the N2 plasma treatment only caused a slight decrease in the intensity of the Si-CH3 peak, while the relative intensity of the mesh-like and cage-shaped Si-0 peaks had little change, suggesting that the Qin plasma could only cause a few si-CH3's bond breaking, but it is not easy to promote the conversion of cage Si-0 to network Si-0; therefore, the bonding conversion behavior of N2 plasma to H0SP low-k film is better than that of H2 and 〇. 2 Plasma has obvious differences. Figures 2 (a) and 2 (b) show that after H2, N2 and several ratios of N2 / H2 mixed atmosphere (20% N2-8m to 80 hops -20 fine 2 ) Of plasma Si-O peak intensity ratio (Iw) and cage-shaped Si-0 to the peak intensity ratio of network Si-O (IN / C); solid dots are the same and quite high- Energy (100W / 9 minutes) after plasma treatment results, the remaining experimental data points are the results of reducing plasma power or energy. Figure 2 illustrates that changes in the plasma atmosphere will result in very different bonding transitions. The 100 W / 9 minute H2 plasma treatment will not only destroy the CH3 side chain of the film, 11 1240967

Also, a large amount of cage-shaped Si-〇 will be shown. These cage-like Si-O, si-C, but gradually increased N2 addition caused Isi-c / si-. The decline is ~ 25%, as shown in Figure 2 (a), and it is transformed into mesh Si-0, which increases IN / C by ~ 50%. As shown in Figure 2 (b), the weakening of the low-polarization bond is even. It is not conducive to the low-k constant characteristics of H0SP. The flow of gas Nucor mixed with Si_⑽ broken axis _ Yu Gangnuo transition, especially when N2 is greater than 60%, the destruction of Si-O and Si-C quickly becomes slow.

In particular, a circle of 2-20% can also be combined with a 6 minute plasma treatment to achieve the optimal effect to achieve the suppression of the passivation of the bond destruction by the 02 plasma. (As described later, this optimized plasma treatment can also be a good idea.

The function of diffusion. ) In order to illustrate the passivation effect of ion nitridation, the invention uses 60, 80, and 100% three high nitrogen content plasmas to perform a plasma purification treatment of H0SP low-k films for 50W / 6 minutes, and then strongly Oxygen plasma (150W / 5min) "attacks" and aFTIR analyzes IsMysi_. The change in the ratio with ㈣ is shown in Figure 3. Obviously, once the newly cured Hosp film is exposed to the oxygen electro-paste environment, its bond will be severely damaged (in accordance with the results in Figure 1). ; Plasma treatment with 10000 / 〇N2 or 60% N2-40% H2 is still not enough to protect HOSP against oxygen plasma attack. Therefore, these films will still be damaged by the oxygen plasma and cause ^^. The significant decrease is shown in Figure 3 (a), and the rise of In / c is shown in Figure 3 (b); however, when N2 / H2 is adjusted to a ratio of 80% -20%, the plasma The low-k film after nitriding can resist the subsequent attack of the oxygen plasma, and maintain the ISi-C / Si- equivalent to the just-cured film. And IN / C ratio. 12 1240967 Table 2 shows the H0SP low-k film immediately after 〇2 (150W / 5 minutes), N2 / H2 (50W / 6 minutes), or N2 / H2 (50W / 6 minutes) plus 〇2 (150W / 5 minutes ), Or N2 / H2 (100W / 3 minutes) Immediately add the FTIR intensity ratio (ISi-c / Si_.) And ιN / 〇 and dielectric constant data after plasma treatment of 〇2 (150W / 5 minutes). N2 /% mixed atmosphere are optimized ratio: 80% -20%. Isi-c / si-o and In / c of newly cured H0SP film are both quantified and defined as 1.0 ×, and measured by CV The obtained dielectric constant is 2.5 'after the plasmon treatment of 02', and its ISi-c / SH) is only 0.74 (that is, the Si-C bond decays sharply); In / c rises sharply to 2.03; These results show that the 02 plasma will have the following destructive effects: promote the transformation of cage-shaped Si-O to reticulated Si-O, leading to a sharp rise in Iswysi-o; destroying the side chain of Si-CH3, causing Isi -c / si-o decline; eventually the dielectric constant of H0SP rises from 2.50 to 3.20, but after the optimization ratio (80% N2-20% ¾), the optimal conditions (50W / 6 Minutes) after plasma treatment, Isi-c / SM) and Ιν / c of the test piece and H0SP just cured The test piece is equivalent, and its dielectric constant has not increased, and remains at 2.50. Moreover, the ion-nitrided test piece can also maintain stable bonding and a good low Ji after a 02 plasma attack. Characteristics (k = 2.51); however, if the plasma power and processing time are changed to deviate from the optimal conditions, even after the ion nitriding of the same input energy (for example: 100W / 3 minutes), the test piece It can't effectively resist the invasion of 02 plasma, so ISi-d0, In / c and dielectric constant are still far from the original value (as shown in Table 2). 13 1240967 Table 2 Quantitative FTIR bonding data (Isi-C / Si-0, In / C) and dielectric constant test condition bonding data / dielectric constant 丄 Si of H0SP film after curing and various plasma treatments -C / Si-0 In / ck Just cured 1.00 1.00 2.50 02 (150W / 5 points) 0.74 2.03 3.20 N2 / H2 (50W / 6 points) 0.96 1.17 2.50 N2 / H2 (50W / 6 points) + 〇2 0.99 1.20 2.51 N2 / H2 (100W / 3 points) + 〇2 0.84 1.36 2.70 Figure 4 is the electric field intensity curve of the leakage current of several types of Cu-gate MIS capacitors. ) 〇2, (c) N2 (50W / 6 minutes) and then go through 〇2, ⑷ 80 jump -20 ° Hui (50W / 6 minutes) and then through 〇2 electropolymerization and (e) 80m-20m ( 〇〇w / 3minutes) H0SP low-k thin film treated with 〇2 plasma as dielectric layer, 〇2 plasma treatment is ι_ / 5 minutes; curves (a) and (b) show: 〇2 The leakage current value of the MIS device treated with the H0SP dielectric layer by plasma treatment is about two stages higher than that of the MIS device using the newly cured H0SP dielectric layer, and the dielectric constant has also increased from 2.50 to 3.20 (as shown in Table 2). ). These data confirm that & Plasma severely alters the bonding of Hosp films and degrades their low-k and electrical insulation characteristics. H2 and N2 electropolymerization in two single atmospheres will not only cause bond damage to the jjQsp film (as shown in Table 2), but also fail to produce an effective passivation effect, so the leakage current value is increased by about one order, as shown in Figure 4. The middle curve (c) is shown. Appropriate Qin / Qin plasma treatment (50W / 6 minutes) will hardly affect the characteristic bonding of low-k films, and will produce a surface passivation effect, so that the H0SP film that has been attacked by 0 2 plasma can still be maintained and rigid. The low-k value of the size of the solidifier-its k value is still 2.5 'and the leakage current is close to that of the solidified test piece. Please compare the curve (a) 14 1240967 and ⑷ in Figure 4. However, if the power / energy wheel If it is improperly inserted (for example: 100w / 3 minutes), the hybrid plasma can not produce good ship performance. Therefore, such threat elements also show a serious leakage current increase after the mystery wire attack, as shown in Figure 4. Curve (e). The above comprehensive analysis of FTIR, I-V, and dielectric constant is true ... Only an optimized ion nitriding treatment (NΛ = 80% / 20%, 50W / 6 minutes) can produce an effective passivation effect. Synchrotron radiation χ light absorption near-structure analysis shows that these effects are attributed to the nitrogen / carbide passivation layer formed on the surface of the Hosp film.

Figure 5 (a) shows the absorption energy spectrum of N (~ 396 to 414eV); Figure 5⑻ shows the absorption energy spectrum of C (280 to 310eV); the H0SP film after NVH2 plasma treatment will obviously be ~ 4. A characteristic absorption peak of N is generated near 〇eV (the main peak is located at 407eV and the secondary peak is at 402.5eV); however, the characteristic absorption peak of N does not exist in the newly cured HOSP test strip; this result confirms: N2 / H2 The passivation and modification of the mixed plasma surface will cause the HOSP film to form a nitride surface layer. In addition, the absorption energy spectrum in Figure 5 (b) shows that the newly cured HOSP test piece will show CH and Si because of its Si-CH3 side chain. -C Two characteristic absorption peaks (peaks at 288 · leV and 288 · 9eV, respectively). [Note: X-ray absorption energy spectrum analysis indicates that the positive thermally oxidized Si0 2 film does not have c- 具有 and Si-C absorption peaks but has the same CC (293 · OeV) and C = C ( The π bond and the σ bond are located at 284.8, ~ 296. 5eV) absorption peaks respectively, so we judge that the absorption peaks of CC and C = C in Fig. 5 (b) are mainly caused by residual carbon in the vacuum environment. ] However, after a short passivation treatment of 50W / 4 minutes, the 〇Η, Si-C gradually widened and shifted to high energy. With the further increase of the processing time, the C- 峰 peak will be more significantly weakened, broadened, and shifted to higher energy. After the 10-minute passivation treatment, the C_H and Si-C 鐽 junction peaks of H0SP are almost Replaced by newly derived CN bond (peak 289.2eV). Comprehensive analysis of these high-resolution X 15 1240967 light absorption spectroscopy analysis confirmed that: N2 / H2 mixed plasma surface passivation and modification treatment can eventually induce

The formation of Si-N / Si-CN passivation layers. These surface nitride layers have the function of protecting HOSp thin films. SIMS nitrogen depth distribution analysis shows that there is a nitrogen-containing surface layer in HOsp thin films after ion nitridation. The length of the nitriding process ranges from 10 to 30 nm. Figure 6 shows the secondary ion mass spectrometry (SIMS) depth distribution of three different Cu / HOSP / Si test specimens after annealing at 300 ° C in a nitrogen atmosphere for one hour; these test specimens were (a) just cured, (b) 〇2 and (c) H0SP low-k film after plasma treatment of 80-200m, and remove the copper film on the surface layer with nitric acid aqueous solution before SIMS analysis to increase the resolution; the test piece is annealed Copper will significantly diffuse into the newly cured H0SP low-k film and accumulate at the H0SP / Si interface 'as shown in curve (a) in Figure 6; as shown in curve (b) in Figure 6, after 〇2 The HOSP film after plasma treatment will seriously lose the barrier effect. Therefore, the strongest copper signal will be accumulated inside the jjosp film and the jj〇sp / Si interface (approximately 1 of the newly deposited HOsp test piece). Times); In addition, copper atoms will also pass through the H0SP / Si interface and penetrate into the silicon substrate. These severe copper diffusions are caused by the bond damage caused by the 02 plasma to the H0SP film, and it is the cause The main reason for the large increase in leakage current; however, after ion nitriding (80m-20% ¾electropolymerization) treatment As shown in the curve (c) φ of the Sixth Middle School, except for the presence of copper in the near surface area, the inner layer of the H0sp film has the lowest copper signal (almost equivalent to the background signal), and there is no copper at the H0SP / Si interface. Accumulation, there is no steel in Si, that is, N2 / H2 mixed plasma surface passivation and modification process also has the function of suppressing copper diffusion. According to the above examples, it can be known that the passivation and modification treatment of the surface of the low-k thin film / 112 mixed plasma of the present invention can form a passivation layer containing nitrogen 1240967, such as Si_c_N / Si_N, on the surface of a typical siloxane low-k film. To achieve the effect of protecting the low-k film, the existence of this passivation layer can prevent the bond damage, the dielectric constant and the current of the typical Wei-based low-k film from rising seriously, and can also have the ability to hinder the diffusion of copper atoms. Therefore, the ultra-thin passivation layer produced on-site by this kind of process will replace the high-resistance ion-deposition TaN and TiN “heterogeneous” diffusion barrier layer and high-dielectric Si—c # cover layer, which can be applied in the future. Microelectronics Nano 1C element. The above detailed description is a specific description of one of the feasible embodiments of the present invention, but this embodiment is not intended to be the exclusive continuation of the present invention. Any equivalent implementation or change made by Wei Lin in this technical frequency should be It is included in the patent scope of this case. To sum up, this case is the first creator to passivate and modify the surface of the low-k thin film 仏 / Qin hybrid plasma. Not only is it technically innovative, but it can also enhance the above-mentioned multiple effects over conventional items. It should be sufficient The statutory invention patent elements that meet the novelty and progressiveness, apply in accordance with the law, and kindly ask your office to approve this invention patent application, in order to stimulate the invention, to the greatest extent. [References] 1. T. C. Chang, P. T. Liu, Y. J. Mei, Y. S. Mor, T H. Perng, Y. L.

Yang, and SM Sze, J. Vac. Sci. Technol. B, 17, 2325 (1999). 2. JJ Kim, Η. H. Park, and SH Hyun, Thin Solid Films, 377-378, 525 (2000) 3. JM Shi eh, KC Tsai, BT Dai, SC Lee, CH Ying, and YK Fang, J. Electrochem. Soc ·, 149, G384 (2002) · 4. M. Du. RL Opial, VM Donnelly, J . Sappjeta, and T. Boone, J.

Appl. Phys., 85, 1496 (1999). 17 1240967 5. SH Yang, H. Kim, and JW Park, Jpn. J. Appl. Phys., 40, 5990 (2001). 6. ST Chen, GS Chen , TJ Yang, TC Chang, and WH Yang, Electrochem. Solid State-State Lett., 6, F4 (2003).

18 1240967 [Schematic description] Figure 1 shows the passivation leaves of the H0SP low-k film after (a) curing and (b) H2 plasma, (c) 〇2 plasma and (d) N2 plasma treatment. Transformed infrared spectrometer (FTIR) spectrum; Figure 2 (a) and Figure 2 (b) are the FTIR spectrum analysis results of H0SP low-k film after Qin / plasma treatment with different input power and various mixing ratios ... (a ) IsKysi •. And (b) In / c; Isi-C / Si-0 and In / c of the original test strip are both defined as normalized values 1; Figures 3 (a) and 3 (b) are the ratios of just cured and passed through various ratios. (A) 1_b of H0SP low-k film after plasma treatment in a krypton / fast mixed atmosphere, and then attacked by 02 plasma. And (b) In / c; Figure 4 is the electric field intensity curve of the leakage current of MIS capacitors using different H0SP low-k films; where H0SP low-k films include (a) just cured, (b) 〇2 plasma, (C) N2 plasma (50w / 6 minutes) plus 〇2 plasma, ⑷optimized n2 / H2 Denso (50W / 6 minutes) plus 〇2electropolymerization and (e) N2 / H2 plasma (100W / 3 minutes) plus O2 electric mass; Figure 5 (a) Nitrogen and ytterbium carbon synchrotron radiation ray photon absorption structure energy spectrum of several H0SP low-k films; Figure 6 is copper film deposition The two ion-extracting ion depth distribution filaments obtained after several plasma treatments of H0sp films and further high temperature heat treatment; the cap film is hardened, (b) 〇2 plasma and (c ) Optimized 仏 / Qin plasma treatment. [Description of main component symbols] Yi 19

Claims (1)

1240967-, [Scope of patent application] i. A kind of low dielectric constant relies on surface passivation and modification treatment branch, which is based on surface acoustic modification treatment of low dielectric constant (k) of Shixi oxygen firing. The method is: After placing the thin film test piece in the reaction chamber, a mixed gas of 仏 / 112 with a gas ratio of 80% 仏 2〇% 112 was introduced, and an RF plasma was used to generate an ionized plasma, and the mixture was N2 / H2. Plasma surface passivation and modification treatment of low-k film thin film; after modification treatment with 8_2-2na 2 and about 50W / 6 minutes optimization conditions, the surface of the thin film test piece can be formed & Sense N mixed bond purification layer.