TW200425325A - 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

200425325

[Technical Field to which the Invention belongs]

The invention relates to a plasma surface passivation modification method for a low dielectric constant film, in particular to a N2 / JJ2 mixed electrospray surface passivation modification method for a low-k film surface; the surface will be coated and cured. The second low ^ film substrate is placed in the reaction chamber of vacuum glow discharge, and is evacuated to less than 10-2-10-4 Pa, and then a mixed gas of N2 / H2 is introduced (the pressure is between _ 102-10-1 Pa) and the RF plasma generator is used to produce the plasma. After the low 1 ^ film is treated with this N2 / H2 mixed plasma treatment, a Si_c_N fish si_N nitride-containing passivation layer can be formed on the surface of the film. ^ Thin film in the 苴 = environment (such as: dielectric constant and leakage caused by 02, H2, N2W, k's retreat, to achieve low protection and strengthening! ^ The effectiveness of the film, in addition, can provide as a low-k film and Diffusion barriers between copper thin films. [Previous technology] In order to improve the performance of components, many new materials have been successively manufactured by bulk circuit wafer components. However, due to the differences in properties between materials and :: difficulty, many problems have arisen, among which In order to reduce the interconnect 4 lead green C Interconnect) The resistance-capacitance (R — C) of Unterietal Dielectrics is expected to gradually shift to ^ 2 ^ 4 · 2) to materials with a k value lower than 3; but because the material = stability, mechanical strength, and bond stability The properties are inferior to those of SiG2, so oxygen < photoresist removal, chemical mechanical polishing (CMP) or annealing treatment often leads to: degradation of electrical characteristics and reduction of thermal stability. These degradations are broken. The strictness of the Damascene process for low-k materials and copper wires

200425325 V. Description of Invention (2) ^. 'It also caused that low-k materials could not be fully integrated into the ic process as expected and currently used in low-k / copper processes. Dielectric frost · Conductive cover materials include Ta, TaN, etc., and the M cover layer can provide diffusion resistance Etc .; however, their overall RC delay time for high-k and high-resistance ^ is also reduced, so as the characteristic size of integrated circuits decreases to one hundred nanometers: Low surface passivation 1 " Materials to develop " Site " Making the V-coating process is a very critical issue. In recent years, due to extensive research, most of these studies use a single reactive gas and Passive gas mixing) to generate plasma, including: NH3, N2O, N2, H2 or), 02 for surface passivation treatment, or the use of iron (ch3) 6 containing undercoat iron * (Hexamethyldisilazane, referred to as HMDS · Trimethylchlorosilane (Referred to as TMCS) for the low damage recovery process. However, the use of a single reactive gas will result in the following (1) corrosive (toxic) properties: Because NH3 is corrosive and toxic, special consideration must be given to maintenance, personnel operation, and waste discharge, so it will be significantly Cause cost and follow-up environmental problems; (2) Thermal Budget: N2 molecule has three of these triple bonds (Three Bonds), so it must be higher 200425325

: Power output or higher substrate processing temperature, which means that the thermal budget is more restrictive: due to the limitation of mono-gas; specific to a low-k film material, it is not suitable for it, it is only suitable for == Applies to a variety of low-k materials, and the passivation of the process window is faced. Therefore, the development of a new low-k film watch process that can overcome the above shortcomings has become the goal of the active efforts of relevant industry players. The invention is to create a mild " environmentally friendly " plasma that is modified and passivated on the surface of N2 / H2 mixed plasma. The plasma has a good compatibility with the microelectronic etching process. Recently, the fluorine gas atmosphere is the most suitable for siloxane dielectric materials. Commonly used dry etching gas, but based on environmental protection requirements and restrictions on use and increasing operating costs, this type of etching gas shovel has gradually been replaced by other atmospheres, of which N2, jj2, N2 / H2 were once It has been used, and N2 / H2 has the most potential. [卜 ^]

In view of the existing single-atmosphere plasma passivation, there may be one or more of the aforementioned shortcomings. Based on the material background and accumulated years of R & D experience in microelectronic thin films and copper processes, the inventor actively researched a treatment method different from a single plasma. (In order to avoid the above-mentioned shortcomings), to solve the problem of degradation of low-k material properties that the industry is desperate to overcome, after continuous trials and experiments, it was found that the / 112 mixed plasma has a synergistic surface modification effect, which can be strengthened Electro-physical properties of k thin film (k = 2.5) of Hybrid Organic Siloxane Polymer (H0SP) board. -

200425325 V. Description of the invention (4) _ [Summary of the Invention] Before explaining the present invention in detail, firstly use three examples to focus on three common single-gas (02, H2 and N2) vacuum glow discharge (Glow-discharge) electricity. Effect of slurry treatment on H0SP thin film: Case 1: Oxygen plasma treatment Oxygen plasma treatment will cause the Si-CH3, Si ~ H and C_H of low-k film to break, forming Si suspension bonds (Dangling Bonds), these Suspended bonds can easily be combined with oxygen atoms in other Si -0 bonds to form a Si-〇 network structure. Therefore, the dragon-like Si_〇 of the H0SP film after the '02 electric mass treatment is reduced, and the network Si- As 〇 increases, the Si-CH3, Si-H, and C-Η low-polarity bonding are also greatly reduced. This H0SP thin film treated with 02 plasma will cause low k because of its characteristic bonding damage. Loss of characteristics and significant decline in insulation and physical characteristics. Case 2: Hydrogen plasma treatment The cage-like Si-〇, S i-C Η 3, C-Η bond in H0SP low-k film after hydrogen plasma treatment will be significantly reduced, and its low-k characteristics and electrical insulation And the degradation of physical properties is similar to the treatment of oxygen plasma. This result shows that jj2 plasma can cause Si-CH3, Si-H and C-Η to break like the 02 plasma, forming Si suspension bonds. These suspensions The dangling bond is very easy to generate cross-linking with other si-〇 to synthesize the Si-0 network structure, which causes the degradation of the characteristics of low-k films. Case 3: Nitrogen plasma treatment Nitrogen plasma treatment only resulted in a slight decrease in the Si-CH3 peak intensity of the H0SP low-k film, while the mesh and cage Si-0 peak intensity had little change. This result

200425325 V. Description of the invention (5) Hint: N2 plasma only causes a small number of Si-CH3 bonds to break, but it is not easy to promote the transition between cage-like and mesh-like Si _0 bonds. However, these bond changes will still be negative. Influence of the electrical properties of low-k films. For this reason, the present invention uses a plasma generated from a mixed gas (N2 / H2) that is different from the above three single-atmosphere examples to perform Ion Nitridation surface modification; and used by conventional techniques Compared with a single reactive gas plasma, the method proposed by the present invention has the advantages listed in Table i. · 〃 1 · The low heat phase does not make the heat package easier 2 · High security 3 · High processability 4 · Low Fuck the following 5. Broad pressure

The addition of pre-different H2 can greatly improve the free efficiency of N2. Therefore, in the N2 passivation plasma treatment, the N2 / H2 mixed plasma has a lower quilt. Use N2 plasma, but use N2 / H2 mixed plasma); all steep because of the non-corrosive #, non-toxic characteristics of N2 / H2, it is safer than nh 丨 processing application; process integrity N2 / H2 It is one of the most advanced plasma atmospheres to replace fluorocarbon etching gas, and it is commonly used in industry, so it has excellent binding property;

The operating costs are N 2 and Η 2 and there is no shortage of resources, and the properties are mild, and there are no concerns about the cost of processing. The process depends on the N 2 / Η 2 allows the independent control of the NH 2 and Η 2 gas power, so it can be controlled to produce different proportions of nitrogen and hydrogen This species is read for a variety of low-k materials. = The case is found to be appropriate to adjust the ratio of N2 / H2 gas, plasma excitation "and the plasma treatment time can make H0sp lower 1 ^ thin film produces a good passivity

200425325 V. Description of the invention (6) to achieve the goal of strengthening the dielectric properties. Table 1 Comparison of characteristics of low-k material purification and chaos. Atmospheric thermal budget safety process integration operation cost control light. # N2 high high low low N20 low high high low NH3 low low The high and narrow N2 + H2 is lower and the high and low are wider. In order for your reviewing committee to understand and understand the method and characteristic energy layer of the present invention, examples are provided in detail as follows. Wen Bing [preferred embodiment] σ spin-coated H0SP low-k material on a silicon wafer substrate surface in a nitrogen environment successively at 15 (TC, 200. (: and 30. 00: each baked to remove condensation) The solvent in the adhesive film was then placed in a tube furnace for 77 hours to cure for one hour. This low-k film was tested at 0 C) and was drawn to less than 10-3 P (about 10_5 Τ〇ΓΓ). The 56 MHz RF power supply is connected to the pedestal 1 in the cavity. The plasma atmosphere contains 02, H2, N2 single-gas and various _2 mixed gases, and the mass flow controller adjusts its flow rate and disk ratio. All the electro-mechanics are operated at a radio frequency of 25% and the time is up to 20 minutes. The processed HOSP low film uses Fourier transform infrared light (FTIR) to analyze the intensity changes of its main bonding peaks. The pots are Si-CH3 (1270 cm)), reticulated Si ~ 〇 (104) and cage

Si 〇 (11 30 cm 1) stretching oscillation peaks in order to identify these electric places

200425325 V. Description of the invention (7) The influence of the principle on the film bonding; the capacitance-voltage (CV) and current-voltage (I-V) measurement of the metal-insulator-Semiconductor (MIS) capacitor structural element The effects of plasma treatment on the dielectric constant and insulation properties of low-k materials can be known separately; in addition, X-ray near-edge structure energy spectrum analysis was performed on H0SP with synchrotron light sources to evaluate Surface bonding transformation of H0SP film caused by plasma treatment; SIMS-depth profile of secondary ion mass spectrometry was used to analyze copper heat treatment at various Si / HOSP / Cu (300 ° C, 1 hour) The diffusion behavior of the test piece can be used to evaluate the diffusion inhibition properties of copper by the H0SP thin film after 02, H2, N2 and N2 / H2 plasma treatment. Figure 1 shows the FTIR spectra of H0SP low-k films after (a) curing and (b) H2, (c) 02, and (d) N2 plasma treatment; these plasma treatments are all 100W / 9 minutes, all The maps include three main bonding peaks of network Si-〇, cage si_〇 and Si -CH3, and two weaker Si-Η

(2240 cm-1) and CH (2970 cm-1) peaks; comparing the spectra (a) and (b), we know that the H0SP low-k thin film network and cage Si-0 bond after H2 plasma treatment Both the position and intensity of the peaks have changed significantly. At the same time, the Si-CH3 and Si-Η bond strengths have also decreased significantly. These results show that the jjqsp low-k film will suffer considerable damage from the Η2 plasma, 〇2 and Η2 H0SP after plasma treatment shows similar bonding transition patterns, as shown in (b) and (c) in Figure 1. This result shows that H2 plasma has a similar destructive effect as 02 plasma, which can cause Si-CH3 Broken bonds with Si-Η form Si suspension bonds, and these Si suspension bonds will then form Si-〇 mesh bonds with other Si-0

Page 13 2 (00425325 V. Description of the invention (8) --- Structure 'Therefore, the cage-shaped Si-O of H0SP film after H2 plasma treatment is reduced, and the mesh-shaped Si-0 is increased; compare Figure 1 (a) And (d) It is learned that the N2 galvanic treatment only causes a slight decrease in the intensity of the Si-CH3 peak, while the relative intensity of the mesh and cage si-0 peaks has little change, suggesting that the N2 plasma can only cause a small amount of Sl-CH3 However, it is not easy to promote the conversion of cage Si-O to reticulated Si-〇; therefore, the bonding conversion behavior of H2SP low-k film by N2 plasma is significantly different from that of H2 and O2.

Figure 2 (a) and Figure 2 (b) show the electric and Si-0 peaks of the H2 / N2 and N2 / H2 mixed atmosphere (20% N2-80% H2 to 80% N2-20% Η2) in several ratios. The ratio of the total intensity (ISi-c / Si-〇) and the peak intensity ratio (IN / C) of the cage Si-0 to the net Si: 0; the solid dots are all the same and quite south energy (100W / 9 minutes), the results obtained after the plasma treatment, and the remaining experimental data points are the results of reducing the plasma power or energy; Figure 2 illustrates that the change in the plasma atmosphere will lead to a very different bond transition phenomenon. The 100W / 9 minute H2 plasma treatment will not only destroy the CH3 side chain of the film, and cause ISi-C / Si-0 to decline to ~ 25. %, As shown in Fig. 2 (a), and a large amount of cage-shaped Si-O will also be transformed into network Si_0, so that 0 / (: increased by ~ 50%, as shown in Fig. 2 (b). The weakening of these cage-like Si—0 and low polarization polarization bonds is not conducive to the low-k constant characteristics of HOSP, but gradually increasing the flow rate ratio of N2 added gas can gradually ease the destruction and avoidance of Si—C. The transformation of dragon-like / reticulated Si-O 'especially when N2 is larger, the destruction of si-〇 and Si ~ c quickly becomes slower', so the ratios of ISi-C / Si-O and in / C are approaching And just cured film. In addition, Figure 2 also shows: Only the three process parameters of N2 / H2 gas ratio, plasma power, and input energy can be properly adjusted.

59S Page 14 200425325 V. Description of the invention (9) 'The side effect is sufficient to produce a protective effect, especially 80% 2-2 %% H2 combined with 50% / 6 minutes processing can achieve the optimal effect to It can suppress the passivation of bond damage caused by plasmon. (As described later, this optimized plasma treatment can also generate a good passivation effect, so that H0SP maintains good dielectric and insulation properties, and at the same time can have a function of blocking copper diffusion.) In order to explain the ion nitridation Passivation effect, creation The present invention uses three high nitrogen content plasmas of 60, 80 and loo% to plasma passivate the H0SP film for 50 ff / 6 minutes, and then subject it to a strong oxygen plasma (150W). / 5 minutes) " attack ", and then FTIR analysis of the change in the ratio of ISi-c / Si_〇 to IN / C, the results are shown in Figure 3. Obviously, once the newly cured HOSP film is exposed to the oxygen plasma After the environment, the bond is severely damaged (results and figures are the same); the use of 100% N2 or 60% N2-40% H2 plasma treatment is still not enough to protect HOSP against the attack of oxygen plasma . Therefore, 'these films will still be damaged by the oxygen plasma, and cause a significant decrease in ISi-C / Si-O, as shown in Fig. 3 (a), and an increase in in / C, as shown in Fig. 3 (b). Shown; however, when N2 / H2 is deployed to 80 ° /. At a ratio of -20〇 / 〇, the low-k film after this plasma nitridation can resist the subsequent attack of the oxygen plasma 'and maintain ISi-C / Si-〇 and 〇 / (: Table 2 shows the H0SP low-k film immediately after 02 (1 50W / 5 minutes), N2 / H2 (50W / 6 minutes), or N2 / H2 (50W / 6 minutes) plus 0 (150W / 5 minutes) ), Or n2 / H2 (100W / 3 minutes) plus 〇2 (150W / 5 minutes) immediately after FTIR intensity ratio (ISi-C / Si-0 and IN / C) · and dielectric constant after plasma treatment Data. N2 / H2 mixed atmosphere is optimized

6 machine page 15 200425325

Ratio: 80% -20%. The ISi-C / Si-〇 and ^ "of the freshly cured Hosp thin film are both quantified and defined as 1.0. The dielectric constant obtained after c-v measurement is 2.5, and then 〇2 After plasma treatment, its ISi_c / Si—〇 has only 0.74 (that is, the si-bond has declined sharply); IN / C has risen sharply to 2.03; these results show that 02 plasma will produce the following damage Effect · Promote the transformation of cage-shaped Si—0 to reticulated Si—O, leading to a sharp rise in iSi-C / Si-O; destroying the side chain of Si_CH3, causing the decline of ISi-C / Si-0; eventually leading to H. The dielectric constant of sp increased from 2.50 to 3.20, but after plasma treatment with optimized ratio (80% N2-20% H2) and optimal conditions (50FF / 6 minutes) The ISi-C / Si-0 and IN / C of this test piece are equivalent to those of the newly cured HOSP thin film test piece, and their dielectric constant has not increased, and still maintained at 2.5 · (), and this ionic nitrogen The chemical test piece can also maintain stable bonding and good low-k characteristics (k = 2 · 5 1) after 02 plasma attack. However, if the plasma power and processing time are changed, the deviation will be optimized. Condition, even after passing through the same input (For example: 10Off / 3 minutes) after ion nitridation, the test piece could not effectively resist the damage of 02 plasma, so that ISi-c / si_〇, IN / C and dielectric constant were still much larger than the original value. Gap (as shown in Table 2). Table 2 Quantitative 2FTIR bonding data (ISi-C / Si-0, IN / C) and dielectric permittivity of HOSP film after curing and various plasma treatments. Data / Dielectric Constant ISi-C / Si-OIN / Ck Rigid 1.001.002. 50 02 (1 50 W / 5 points) 0 · 742 · 033 · 20 N2 / H2 (50 W / 6 points) 0 · 961 · 172 · 50

Page 16 200425325 V. Description of the invention (11) N2 / H2 (50 W / 6 points) +02 0 · 991 · 202 · 51 N2 / H2 (100 W / 3 points) + 020 · 841 · 3 62 · 70 Figure The fourth is the electric field intensity curve corresponding to the leakage current of several Cu-gate MIS capacitors. It is calculated using (a) just solidified, (b) 〇2, (c) N2 (50W / 6 minutes), and then passed. 2, (d) 80% N2-20% H2 (50W / 6 minutes) and then 02 plasma and (e) 80% N2-20% H2 (100W / 3 minutes) and then treated with 02 plasma HOSP low The k film is used as a dielectric layer, and the 〇2 plasma treatment is 150W / 5 minutes, and the curves (a) and (b) show: 〇2 plasma treatment H〇sp

The leakage current value of the MIS element of the dielectric layer is about two orders of magnitude higher than that of the MIS element using the newly cured H0sp dielectric layer, and the dielectric constant has also increased from 2.50 to 3.40 (as shown in the table) 2). These data confirm that the 02 plasma will severely change the bonding of the H0SP film and detract from its low-k and electrical insulation characteristics.单一 2 and ⑽ two single atmosphere plasmas will not only cause the bond damage of H0SP 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 curve (c) shows. The proper N2 / H2 plasma treatment (50W / 6 minutes) will hardly affect the characteristic bonding of the low-k film, and it will produce a surface passivation effect, which will be attacked by a 02 plasma. The H0SP film can still maintain a low k value that is comparable to that of the just-cured person-its ^ value is still 2.5, and the leakage current is close to the just-cured test piece. Please compare the curves (a) and (d) in Figure 4; However, if the power / energy input is improper, such as: 100W / 3 minutes), the N2 / H2 mixed plasma cannot produce good chemical properties. Therefore, such MIS components also show a serious increase in leakage current after the 02 plasma attack. See the curve in Figure 4. Above? Comprehensive analysis of 1 '"and Bu v and dielectric constant confirm that:

200425325 V. Description of the invention (12) Optimized ion nitriding treatment (N2 / H2 = 80% / 20%, 50ff / 6 minutes) can produce effective passivation effect. Analysis of the structure of synchrotron X-ray absorption near-edge shows that these effects are attributed to the nitrogen / carbide passivation layer formed on the surface of the H0SP film. Figure 5 (a) is the absorption spectrum of N (~ 3 96 to 414eV); Figure 5 (b) is the absorption spectrum of C (280 to 310eV) • After N2 / H2 plasma treatment

The H0SP film will obviously produce a characteristic absorption peak of N around ˜400 eV (the main peak is at 407 eV and the secondary peak is at 402.5 eV); however, the characteristic absorption peak of N does not exist in the newly cured H 〇SP test strips; this result confirms that: passivation and modification of the surface of the N2 / H2 mixed plasma will cause the 〇SP thin film to form a nitride surface layer; in addition, the absorption energy spectrum in Figure 5 (b) shows that the The film will show two characteristic absorption peaks of CH and Si-C (the peaks are at 288 · leV and 288 · 9eV, respectively) because of its Si-CH3 side chain. [Note: X-ray absorption energy spectrum analysis confirms that the thermally oxidized Si0 2 film does not have the absorption peaks of CH and Si-C but has the same CC (293.0eV) and C = C (P bond and The s-bonds are located at 284 · 8 and ~ 296.5eV, respectively. Therefore, we determine that the CC and C = C absorption peaks in Figure 5 (b) are mainly caused by residual carbon in the vacuum environment. ] But after a short time passivation treatment of 5 Off / 4 minutes, its C-H and Si-C gradually widened and shifted toward high energy. With the further increase of the processing time, the C-Η peak will be more significantly weakened, broadened, and shifted to higher energy. After 10 minutes of passivation treatment, the C-H, Si- The C-bond peak was almost replaced by the newly derived cN-bond (peak 289 · 2eV). Comprehensive analysis of these high-resolution X-ray absorption spectroscopy confirmed that: N2 / H2 mixed plasma surface passivation and modification treatment can finally induce Si-N / Si-C-N

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The formation of purification layers, these surface nitride layers have the function of protecting HOSp thin films; SIMS nitrogen depth distribution analysis shows that there is a lice-containing surface layer on the HOSp thin films after ion nitriding, depending on the length of the ion nitriding treatment, Its thickness ranges from 10 to 30 nm.

Figure 6 shows the secondary ion mass spectrometry (SIMS) depth distribution of three different Cu / H0SP / 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 thin film after 80% N2-20% H2 plasma treatment, and remove the copper film on the surface layer with an aqueous solution of acid before the SIMS analysis to increase the resolution; After annealing, copper will significantly diffuse into the newly cured H0sp film and accumulate at the HOSP / Si interface, as shown in curve (a) in Figure 6; as shown in curve (b) in Figure 6 The H0SP film after 〇2 plasma treatment will seriously lose the barrier effect. Therefore, the strongest copper signal will be accumulated inside the HSp film and the HOSP / Si interface (about 10 times of the newly deposited H0SP test piece). ); In addition, copper atoms will also pass through the HOSP / Si interface and penetrate into the silicon substrate. These severe copper diffusions are caused by the bond damage caused by the 02 dendrite to the H0SP thin film and cause leakage current. The main reason for the sharp rise; however, after ion nitriding (80% N2-20M2 plasma) After processing, the picture is shown in the sixth curve (c), except for the 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 HOSP / Si interface. The accumulation of 2 and the absence of copper in the interior, that is, the surface passivation and modification of the N2 / H2 mixed plasma also has the additional function of suppressing copper diffusion. It can be known from the above examples that the N2 / H2 of the low-k film proposed by the present invention

Page 19 200425325 V. Description of the invention (14) The surface of the mixed plasma is purified and modified, which can protect the low-k thin film formation in thin, broken 1 and other rabbit-containing passivation layers. The existence of this passivation layer can It prevents the damage of the H0SP low 1 ^ film from being broken, the dielectric constant and the leakage current being severely increased. It also has the ability to hinder the diffusion of copper source and ions. Therefore, this process is ultra-thin The passivation layer will replace the high-resistance sputter deposition TaN, TiN " heterogeneous " diffusion barrier layer and high-dielectric Si-C coatings, etc., which can be applied to the future microelectronics nano 1 (: component 0 above) Yang Xi 5 Youming is a specific description of a feasible embodiment of the present invention. This embodiment is not intended to limit the scope of the patent of the present invention. Any equivalent implementation or change that does not depart from the technical spirit of the present invention should include In the scope of the patent of this case. To sum up, 'This case is the first creator to passivate and modify the surface of n2 / H2 mixed plasma of low-k film. It is not only innovative in terms of technical ideas, but also can be improved compared with conventional articles. Many of the above effects should be charged Patented invention meets the statutory requirements of novelty and progressiveness, the Yuan proposed the law to apply, ask your Board approved this patent application for inventions, to encourage invention, sense of ethics to it. [References]

1 · T · C · Chang, P · T · Liu, Y · J · Mei, Y · S · Mor, T · ze · Perng, Υ · L · Yang, and S · M · Sze, J · Vac ·

Sci · Technol · B, 17, 2325 (1999) · 2. J.J · Kim, Η · H · Park, and S · H · Hyun, Thin

Solid Films, 377-378, 525 (2000) 3. J. M. Shieh, K. C. Tsai, B. T. Dai, s. C. Lee,

Page 20 200425325 V. Description of Invention (15) C. H. Ying, and Y. K. Fang, J. E1 ectrochem.

Soc ·, 149, G384 (2002). 4.M, Du. RL Opial, VM Donnelly, J. Sapp j eta, and T. Boone, J. Appl. Phys., 85, 1496 (1999). 5.5. H . Yang, H. Kim, and JW Park, Jpn. J.

Appl. Phys., 40, 5990 (2001). 6.5. T. Chen, G. S. Chen, T. J. Yang, T. C. Chang, and W. H. Yang, E1 ectrochem. Solid State-State

200425325 Brief description of the drawing Figure 1 shows the transmission leaf conversion infrared spectrometer of H0SP low-k film (a) just cured and treated with (b) H2 plasma, (c) 02 plasma and (d) N2 plasma. FTIR) spectrum; Figures 2 (a) and 2 (b) are the FTIR spectrum analysis results of H0SP low-k films after N2 / H2 plasma treatment with different input power and various mixing ratios: (a) ISi-C / Si-0 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 just cured and passed (A) ISi-C / Si-O and (b) IN / C of H0SP low-k thin film of 02 / H2SP attack after plasma treatment of N2 / H2 mixed atmosphere in various ratios; Figure 4 shows the use of different H0SP The leakage current of the low-k film M IS capacitor element corresponds to the electric field strength curve; the H0SP low-k film includes (a) just cured, (b) 02 plasma, (c) N2 plasma (50W / 6 minutes) plus 〇2 Electropolymerization, (d) Optimized N2 / H2 Plasma (50 W / 6 minutes), plus 〇2 Plasma and (e) N2 / H2 Plasma (100FF / 3 minutes). 〇2 Electropolymerization;

Fig. 5. Spectra of (a) nitrogen and (b) carbon synchrotron radiation X-ray absorption near-structures of several H0SP low-k thin films; six is a steel film deposited on several different plasma-treated H0SP thin films and then subjected to high temperature Depth distribution of secondary copper ions obtained after heat treatment; of which H0SP

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Claims (1)

200425325 1. One type of plasma surface passivation modification method for a dielectric constant film is to perform surface passivation modification of a low-oxygen burned " electric constant (k) film. The f method is to place this film test piece on After the reaction chamber, the N2 / H2 mixed gas is introduced and an RF plasma is used to generate an ionized plasma. The N2 / H2 mixed plasma is used to perform plasma surface passivation and modification on the low-k film test piece. After the modification of the chemical conditions, a mixed bonding passivation layer of Si-CN and Si-N can be formed on the surface of the thin film test piece. 2. The plasma surface passivation modification method for the low-dielectric-constant film described in item 1 of the scope of the patent application, wherein the surface passivation layer can prevent subsequent high-oxidation or reducing plasma processes, and The damage caused by the low-polarity chemical bonding and the dielectric constant can be used to protect and strengthen the low-k film. 3. The plasma surface passivation modification method for the low dielectric constant film described in item 1 of the scope of the patent application, wherein the passivation layer can also serve as a diffusion barrier layer to alleviate the thermal diffusion phenomenon of copper to the low-k film. Avoid using dielectric materials with high dielectric characteristics or high-resistivity metal diffusion barrier materials, which will increase the overall resistance-capacitance (R_C) delay time of the connecting wires inside the integrated circuit components and reduce the computing performance of the components. 4. The plasma surface passivation modification method for the low dielectric constant film described in item 1 of the scope of the patent application, wherein the N27H2 gas ratio can be 20% N2-80% H2 to 80% N2-20% H2 ° 5. The plasma surface passivation modification method for the low dielectric constant film described in item 1 of the scope of the patent application, wherein the N2 / H2 gas ratio of 80% N2_20% H2 combined with 50W / 6 minutes treatment can achieve the best The effect. Page 24 200425325 Page 25