• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The polishing felt is intended for planarization of at least one of semiconductor, optical and magnetic substrates. The polishing felt comprises a cast polyurethane polymer material formed from a H12MDI / TDI prepolymer reaction with polytetramethylene ether glycol to form an isocyanate-terminated reaction product. The isocyanate-terminated reaction product has from 8.95 to 9.25 weight percent unreacted NCO and has a stoichiometric NH 2 to NCO ratio of 102 to 109 percent. The isocyanate-terminated reaction product is cured with a curing agent of 4,4'-methylenebis (2-chloroaniline). The cast polyurethane polymer material, as measured in a non-porous state, has a shear storage modulus, G 'of 250 to 350 MPa as measured with torsional fixation at 30 ° C and 40 ° C and a loss modulus shear strength, G "of 25 to 30 MPa as measured with a twist fixation at 40 ° C. The polishing felt has a porosity of 20 to 50 percent by volume and a density of 0.60 to 0.95 g / cm 3 .
    公开号:FR3024955A1
    申请号:FR1557800
    申请日:2015-08-19
    公开日:2016-02-26
    发明作者:Bainian Qian；Jr Raymond L Lavoie；Marty Degroot；Benson Lee
    申请人:Rohm and Haas Electronic Materials CMP Holdings Inc；Dow Global Technologies LLC；Rohm and Haas Electronic Materials LLC；
    IPC主号:
    专利说明:

    [0001] BACKGROUND OF THE INVENTION This disclosure relates to polishing felts useful for polishing and planarizing substrates and particularly planarizing polishing felts having accelerated metal removal rates with low levels of defects. Polyurethane polishing felts are the main type of felt for various precision polishing applications. These polyurethane polishing felts are effective for polishing silicon wafers, patterned wafers, flat panel displays, and magnetic storage disks. In particular, polyurethane polishing felts provide mechanical integrity and chemical resistance for most polishing operations used to manufacture integrated circuits. Polyurethane polishing felts, for example, have high strength to resist tearing; abrasion resistance to avoid wear problems during polishing; and stability to resist attack by strong and strong caustic acid polishing solutions.
    [0002] Semiconductor production typically involves several chemical mechanical planarization (CMP) processes. In each CMP process, a polishing felt in combination with a polishing solution, such as a polishing slurry containing an abrasive-free abrasive or reagent liquid, removes excess material to planarize or maintain planarity for receive a subsequent layer. The stack of these layers combines to form an integrated circuit. The fabrication of these semiconductor devices continues to become more complex due to requirements for devices with higher operating speeds, lower leakage currents and reduced power consumption. In terms of device architecture, this results in finer relief geometries and higher metallization levels. These requirements of increasingly stringent device designs are leading in some applications to the adoption of a greater number of tungsten interconnection vias or vias in combination with new dielectric materials having lower dielectric constants. The decreased physical properties, frequently associated with low k and ultra-low k materials, in combination with the higher complexity of the devices have led to greater requirements on CMP consumables, such as felts. polishing and polishing solutions. Low k and ultra-low k dielectrics particularly tend to have lower mechanical strength and poorer adhesion compared to conventional dielectrics, making planarization more difficult. In addition, as the dimensions of the reliefs of the integrated circuits decrease, the defectivity induced by the CMP, such as scratches, becomes a larger problem. The reduced film thickness of the integrated circuits further requires improvements in defectivity while simultaneously providing acceptable topography to a wafer substrate - these topographic requirements require ever stricter planarity, concavity and erosion requirements. . Polyurethane casting into cakes and cutting the cakes into several thin polishing felts has been proven to be an effective method for producing polishing felts with consistent, reproducible polishing properties. Kulp et al., In US Pat. No. 7,169,030 discloses the use of high tensile polishing felts to improve planarization while maintaining low defectivity. Polishing properties regarding the metal removal rates and low defectivity required for most demanding low-defect polishing applications are sadly lacking in the polyurethane felts produced from these formulations. DEFINITION OF THE INVENTION An aspect of the invention comprises a polishing felt suitable for planarizing at least one of semiconductor, optical and magnetic substrates, the polishing felt comprising a cast polyurethane polymer material formed from a reaction of the H12MDI / TDI prepolymer with polytetramethylene ether glycol to form an isocyanate-terminated reaction product, the isocyanate-terminated reaction product having from 8.95 to 9.25 percent by weight of unreacted NCO, having a stoichiometric NH 2 to NCO ratio of 102 to 109 percent, the isocyanate-terminated reaction product being cured with a curing agent of 4,4'-methylenebis (2-chloroaniline), the cast polyurethane polymer material, as measured in a non-porous state, having a shear storage modulus, G 'of 250 to 350 MPa as measured with torsional fixation at 30 ° C and 40 ° C and a shear loss module, G "of 25 to 30 MPa as measured with 40 ° twist fixation (ASTM D5279) and the polishing felt having a porosity of 20 to 50 percent by volume and a density of 0, 60 to 0.95 g / cm3. In a particular embodiment, a shear storage modulus ratio, G 'at 40 ° C with shear loss modulus, G "at 40 ° C is 8 to 15. In another particular embodiment, the The isocyanate-terminated reaction product and 4,4'-methylenebis (2-chloroaniline) have the stoichiometric NH 2 to NCO ratio of 103 to 107 percent. In yet another particular embodiment, the polishing felt comprises pores having In yet another particular embodiment, the density is 0.7 to 0.9 g / cm 3. Another aspect of the invention provides a polishing felt suitable for planarization. at least one of semiconductor, optical and magnetic substrates, the polishing felt comprising a cast polyurethane polymer material formed from a prepolymer reaction of H12MDI / TDI with polytetramethylene ether glycol to form an isocyanate-terminated reaction product, the isocyanate-terminated reaction product having from 8.95 to 9.25 weight percent unreacted NCO, having a stoichiometric NH 2 to NCO ratio of from 103 to 107 percent, the isocyanate-terminated reaction product being cured with a 4,4'-methylenebis (2-chloroaniline) curing agent, the cast polyurethane polymer material, as measured in a non-porous state, having a storage modulus of shear, G 'of 250 to 350 MPa as measured with torsional fixation at 30 ° C and 40 ° C and a shear loss modulus, G "of 25 to 302 4 955 4 MPa as measured with a torsion fixation at 40 ° C (ASTM D5279), wherein a ratio of the shear storage modulus, G 'at 40 ° C to the shear loss modulus, G "at 40 ° C is 8 to 15 and the polishing felt having a porosity of 20 to 50 percent by volume and a density of 0.60 to 0.95 g / cm3. In a particular embodiment, a shear storage modulus ratio, G 'at 40 ° C to the shear loss modulus, G "at 40 ° C is 8 to 12. In another particular embodiment, the The isocyanate-terminated reaction product and 4,4'-methylenebis (2-chloroaniline) have the stoichiometric NH 2 to NCO ratio of from about 10 4 to about 10 6 percent, and in one embodiment the polishing felt comprises pores having average diameter from 10 to 60 μm.
    [0003] In still a particular embodiment, the density is 0.70 to 0.80 g / cm 3. DESCRIPTION OF THE DRAWINGS Figure 1 is a bar graph illustrating the improved TEOS dielectric removal rates achieved with polishing felts of the invention. Figure 2 is a plot that illustrates the improved TEOS dielectric and thermal oxide removal rates achieved over a range of slurry rates.
    [0004] Fig. 3 is a diagram illustrating the cross-section of a patterned wafer prior to a chemical mechanical planarization. Figure 4 illustrates the shrinkage material removal required to reduce the stage height with a line / gap ratio (L / S) of 500 μm / 500 dBA.
    [0005] Figure 5 illustrates the shrinkage material removal required to reduce the stage height with a 25 μm / 25 μm line / gap ratio (L / S). FIG. 6 is a measure of the time required to achieve planarization during the polishing of a patterned TEOS wafer.
    [0006] Figure 7 plots the tungsten removal rate as a function of the downward force of the support in kPa.
    [0007] Figure 8 is a bar graph illustrating the improved tungsten removal rate of the invention. DETAILED DESCRIPTION The polishing felt is suitable for planarization of at least one of semiconductor, optical and magnetic substrates. Felt is even more useful for polishing semiconductor substrates. Exemplary wafer substrates, in which the felt has particular effectiveness, include tungsten and TEOS polishing and shallow trench isolation polishing or with suspensions containing cerium oxide particles. . The polishing felt comprises a cast polyurethane polymer material formed from a H12MDI / TDI prepolymer reaction with polytetramethylene ether glycol to form an isocyanate-terminated reaction product. The isocyanate-terminated reaction product has from 8.95 to 9.25 weight percent unreacted NCO and a stoichiometric NH 2 to NCO ratio of 102 to 109 percent. This stoichiometric ratio is preferably from 103 to 107 percent. The isocyanate-terminated reaction product is cured with a 4,4'-methylene-bis (2-chloroaniline) curing agent. The cast polyurethane polymer material, as measured in a non-porous state, has a shear storage modulus, G 'of 250 to 350 MPa, as measured with torsional fixation at 30 ° C and 40 ° C and a modulus of shear loss, G "of 25 to 30 MPa, as measured with 40 ° C torsion fixation (ASTM D5279) at a frequency of 10 rad / sec and a temperature ramp of 3 ° C / min. felt preferably has a shear storage modulus ratio, G 'with a shear loss modulus, G "of 8 to 15, as measured with torsional fixation at 40 ° C. The felt still has a shear storage modulus ratio, G 'with shear loss modulus G' of 8 to 12 as measured at 40 ° C. This equilibrium between the shear storage module and the shear modulus Shear loss provides an excellent combination of high shrinkage speed with low defectivity.
    [0008] The polymer is effective for forming porous or filled polishing felts. For purposes of this disclosure, the filler for polishing felts comprises solid particles which dislodge or dissolve during polishing, and particles or spheres filled with liquid. For purposes of this disclosure, the porosity comprises gas-filled particles, gas-filled spheres, and voids formed from other means, such as by mechanically bubbling gas into a viscous system, injecting gas in the polyurethane melt, introducing gas in situ using a chemical reaction with a gaseous product, or reducing the pressure to cause the dissolved gas to form bubbles. The porous polishing felts contain a porosity or a filler concentration of at least 0.1% by volume. This porosity or filler contributes to the ability of the polishing felt to transfer to the polishing fluids during polishing. The polishing felt preferably has a porosity or a filler concentration of 20 to 50 percent by volume. With respect to density, levels of 0.60 to 0.95 g / cm3 are effective. Density levels of 0.7 to 0.9 g / cc are preferably effective. For lower porosity, higher polishing removal rates are lacking in polishing felts. For higher porosity, the rigidity required for demanding planarization applications is lacking in polishing felts. The pores optionally have an average diameter of less than 100 μm. The pores or filler particles preferably have a mass average diameter of 10 to 60 μm. The pores or filler particles even more preferably have a mass average diameter of 15 to 50 μm. Control of the unreacted NCO concentration is particularly effective in controlling pore uniformity for pores formed directly or indirectly with a feed gas. This is because the gases tend to be subjected to thermal expansion at a much higher rate and to a much greater extent than solids and liquids. The method is for example particularly effective for a porosity formed by casting hollow microspheres, either pre-expanded or expanded in situ; using chemical foaming agents; by mechanically bubbling in gas; and using dissolved gases, such as argon, carbon dioxide, helium, nitrogen, and air, or supercritical fluids, such as supercritical carbon dioxide, or formed gases in situ as a reaction product. Examples Cast polyurethane cakes were prepared by the controlled mixture of (a) an isocyanate-terminated prepolymer at 51 ° C (or desired temperatures based on different formulations) obtained by the reaction of a polyfunctional isocyanate (e.g. ie, toluene diisocyanate, TDI) and a polyether-based polyol (e.g. Adiprene® LF750D and others listed in the tables, commercially available from Chemtura Corporation); (b) a curing agent at 116 ° C and optionally (c) a hollow core filler (ie Expancel® 551DE40d42, 461DE20d60, or 461DE20d70, available from Akzo Nobel). The ratio of the isocyanate-terminated prepolymer and the curing agent was set so that the stoichiometry, as defined by the ratio of the active hydrogen groups (i.e. the sum of -OH groups and -NH 2) in the unreacted isocyanate curing agent (NCO) in the isocyanate-terminated prepolymer, was set according to each formulation as listed in the Tables. The hollow core charge was mixed in the isocyanate-terminated prepolymer prior to the addition of a 4,4'-methylenebis (2-chloroaniline) curing agent. The isocyanate-terminated prepolymer with the embedded hollow core charge was then mixed together using a high shear mixing head. After the release of the mixing head, the combination was dispensed over a period of 3 minutes into a circular mold of 86.4 cm (34 inches) diameter to provide a total pouring thickness of approximately 8 cm (3 inches). . The dispensed combination was allowed to gel for 15 minutes before placing the mold in a curing oven. The mold was then cured in the curing oven using the following cycle: 30 minute ramp from oven temperature adjustment point temperature to 104 ° C, then hold for 15.5 hours with an oven adjustment point temperature of 104 ° C, and then a 2 hour ramp of the oven adjustment point temperature of 104 ° C decreasing to 21 ° C. Table 1 comprises the polishing felt formulations made by the above process with different prepolymers, stoichiometries, pore sizes, pore volumes and groove patterns. The cured polyurethane cakes were then removed from the mold and sliced (cut using a moving blade) at a temperature of 30 to 80 ° C into multiple polishing layers having an average thickness of 1.27 mm (50 thousandths). inch) or 2.0 mm (80 thousandths of an inch). Slicing was initiated from the top of each cake. Table 1 lists the main properties of the polishing layer used in this study. The examples of polishing layer felts 1 and 2 were finished with perforations P and perforations plus an AC24 coating (P + AC24), respectively, for better transport of the suspension. The perforations had a diameter of 1.6 mm and a spacing of 5.4 mm in MD and 4.9 mm in XD arranged in a staggered pattern. The AC24 coating is an X-Y or square type pattern having depths of 0.6 mm, width 2.0 mm and not 40 mm. SubaTM 400 (40 mil) was stacked on the polishing layer. The polishing layer for example felt pens 3 and 4 was finished with circular grooves 1010 and K-7, respectively. The grooves 1010 had a width of 0.51 mm (20 mils), a depth of 0.76 mm (30 mils) and a pitch of 3.05 mm (120 mils). K-7 grooves had a width of 0.51 mm (20 thousandths of an inch), a depth of 0.76 mm (30 thousandths of an inch) and a pitch of 1.78 mm (70 thousandths of an inch).
    [0009] Table 1 Felt Prepolymer NCO (% in Stoichiometry NH2 to NCO Size Porosity Groove Weight) of Prepolymer (%) Pore Volume (Pm) (%) 1 Adiprene L325 8.95-9.25 105 20 36.4 P 2 Adiprene L325 8.95-9.25 105 20 36.4 P + AC24 3024 955 9 3 Adiprene L325 8.95-9.25 105 20 33.1 1010 4 Adiprene L325 8.95-9.25 105 20 34, 8 K-7 A Adiprene L325 8.95-9.25 87 40 30.5 PB Adiprene L325 8.95-9.25 87 40 30.5 P + AC24 C Adiprene LF750D 8.75-9.05 105 20 19 , 2 PD Adiprene L325 8.95-9.25 87 20 33.6 1010 E Adiprene L325 8.95-9.25 87 40 31.4 1010 F Adiprene L325 8.95-9.25 105 20 15.7 1010 G Adiprene L325 8.95-9.25 87 20 17.9 1010 H Adiprene L325 8.95-9.25 87 40 30.4 1010 I Adiprene L325 8.95-9.25 87 20 33.0 K-7 J Adiprene L325 8.95-9.25 87 40 29.7 K-7 K Adiprene L325 8.95-9.25 87 40 39.1 K-7 L Adiprene LF750D 8.75-9.05 105 20 16, 1 K-7 M Adiprene LF750D / Adiprene LFG740D (1: 1 by weight) 8.75-9.05 / 95 20 13.0 K-7 8.65-9.05 Adiprene® is a urethane prepolymer product from Chemtura Corporatio Adiprene L325 is an H12MDI / TDI urethane prepolymer with polytetramethylene ether glycol (PTMEG) having from 8.95 to 9.25% by weight of unreacted NCO. Adiprene LFG740D is a TDI urethane prepolymer with ethylene oxide (PPG) capped polypropylene glycol having from 8.65 to 9.05% by weight of unreacted NCO. Adiprene LF750D is a urethane prepolymer of TDI-PTMEG urethane prepolymer having 8.75 to 9.05% by weight of unreacted NCO. Polishing oxide control slab The slurry used was a cerium oxide suspension having a mean particle size of 0.1 μm, diluted with DI water at a ratio of 1: 9 to time of use for polishing. Polishing was carried out on a FREX300 300mm CMP polishing system from Ebara Technologies, Inc. Table 2 below summarizes the polishing conditions.
    [0010] 5 Table 2 FREX300 Polishing Device (Ebara) G2S Head Down Force CAP / RAP / OAP / EAP / RRP / PCP: 500/500/500/500/650/250 [HPa] After Profile Adjustment: 500/500/450 / 400/650/250 [HPa] TT / TP 100/107 [rpm] Flow rate 188 ml / min Polishing time Control / fictitious: 30 s Dresser Asahi Dressing DF = 100N, Table 20 rpm, Dresser 16 rpm, lapping: 600 s, Ex-situ 30 s Two types of oxide slabs were evaluated. These were a chemical vapor deposition formed TEOS oxide slab (TEOS is the tetraethyl orthosilicate decomposition product) and a thermally grown oxide slab (th-SiO 2). The withdrawal rates (VR) of the two types of oxide wafers are shown in Figure 1 and summarized below in Table 3.
    [0011] Table 3 Felt Stoichiometry Porosity Volume Size, VR VR Gyrations of NH2 to NCO Oxides, Thermal TEOS Pores (%) (Pm) (%) (λ / min) (λ / min) 1 105 20 36.4 P 8342 7344 2 105 20 36.4 P + AC24 9303 7976 A 87 40 30.5 P 5875 5074 B 87 40 30.5 P + AC24 6759 5760 C 105 20 19.2 P 6728 5771 It was also evaluated for TEOS oxide slabs, shrinkage rates at different slurry rates, with the results shown in Fig. 2. Polishing felts with 105 percent stoichiometry had higher consistent TEOS removal rates at different suspension rates.
    [0012] 5 Polishing of TEOS pattern wafers Table 4 lists polishing felts used in a pattern wafer study. The slurry used was a cerium oxide suspension having an average particle size of 0.1 μm, diluted with DI water at a ratio of 1: 9 at the time of use for polishing. All of the felts had a 1.27 mm (50 mil) perforated polishing layer and a stacked Suba 400 subfelt. The polishing conditions for a pattern galette study are summarized in Table 5.
    [0013] Table 4 Felt Stoichiometry Porosity Size in Grooves NH2 to NCO, ° A) Pore (pm) Volume, 1 105 20 36.4 PA 87 40 30.5 PC 105 20 19.2 P 3024 955 12 Table 5 Polishing Device FREX300 (Ebara) G2S Head Down Force CAP / RAP / OAP / EAP / RRP / PCP: 500/500/500/500/650/250 [HPa] After profile adjustment: 500/500/450/400/650/250 [HPa] TT / TP 100/107 [rpm] Flow rate 188 ml / min Polishing time Control / fictitious: 10 s Dresser Asahi Dressing DF = 100N, Table 20 rpm, Dresser 16 rpm, Lapping 600 s, Ex-situ 30 s The patterned wafer had a 5,000 Å stage height (MIT-STI-764 pattern) formed by 7,000 Å chemical vapor deposition of TEOS. The cross-section of a TEOS-deposited patterned wafer is shown in FIG. 3. The planarization efficiency was evaluated at a line-to-space ratio (L / S) of the two values 500 μm / 500 μm and 25 μm. / 25 pm. The planarizing efficiency of the felt 1 was found to be better than that of the control felt A and comparable to a less porous and stiffer control felt C, as shown in FIGS. 4 and 5. floor height indicates better planarization efficiency. The felt 1 also had both a high shrinkage speed and a good planarization efficiency. As a result, the polishing time can be significantly reduced during planarization, as shown in FIG. 6. The ratio represents the polishing time for the felt in relation to the control felt A. More the ratio is low, plus the felt is effective to achieve the planarization.
    [0014] Tungsten Control Wafer Polishing Tungsten polishing was performed with 200 mm wafers in a Mirra Tm polishing device manufactured by Applied Materials. The polishing conditions are summarized below for initial evaluation with Cabot tungsten suspension SSW2000. The top felt was 2.03 mm (80 thousandths of an inch) thick, finished with grooves 1010 and a Suba Tm IV sub-felt of thickness 1.02 mm (40 thousandths of an inch). Polishing conditions for 200 mm tungsten slabs: Suspension: Cabot SSW2000 (1: 2 dilution with 2.0% by weight H202 deionized water) Suspension rate: 125 ml / min suspension: - 66 mm from center Conditioning agent: Saesol AMO2BSL8031C1-PM 10 Felt lapping: 113/93 rpm, 3.2 kg-f (7 lb-ft) CDF, 10 total zones, 3600 seconds Ex-situ process: 113/93 rpm, 3.2 kg-f (7 lb-ft), 10 total zones, 10 seconds Groove: 1010 15 Polishing conditions Downward force: 29 kPa (4.2 psi) Tray Speed: 113 rpm Support Speed: 111 rpm Polishing Time: 60 seconds Table 6 summarizes the main felt properties and compares the tungsten removal rate with a Cabot SSW2000 suspension at a dilution of 1: 2 with DI water and 2.0% by weight H 2 O 2.
    [0015] Table 6 Felt Stoichiometry NH2 to NCO, Porosity Size Groove VR of W (%) Pore in (λ / min) (μm) Volume, (%) 3 105 20 33.1% 1010 4349 D 87 20 33.6% 1010 3916 E 87 40 31.4% 1010 3039 F 105 20 15.7% 1010 3380 G 87 20 17.9% 1010 3237 H 87 40 30.4% 1010 2914 302 4 955 14 The tungsten removal rates were significantly higher for felt 3 having a polishing layer for H12MDI / TDI with polishing felts of polytetramethylene ether glycol cured with a curing agent of 4,4'-methylenebis (2-chloroaniline) having a stoichiometry of 105% and 33% in pore volume. Figure 7 shows the felt 3 having higher tungsten removal rates for different downward polishing forces. In a second series of tests, the Cabot SSW2000 suspension was also evaluated at different dilution ratios (1: 1.5 with 10 DI water) and advanced tungsten suspension. The polishing conditions are summarized below. Tool: Applied Mira with Titan SP + head Suspension 1: W2000 (1: 1.5, 2.4% by weight H 2 O 2), 70 ml / min Suspension 2: advanced tungsten suspension (1: 1.8, 2, 0% by weight H202), 100 ml / min Conditioning Disc: 20 Kinik PDA32P-2N (IDG-2) for W2000 3M A3700 Testing for Advanced Tungsten Suspension Testing Recipes with W2000 Felt Lapping: 113 / 93 rpm, 5.0 kg-f (11 lb-ft) CDF, 25 total zones, 30 minutes Polishing: 113/111 rpm, 29 kPa (4.2 psi), 60 sec, 70 ml / min Packaging: ex-situ: 113/93 rpm, 5.0 kg-f (11 lb-ft) CDF, 10 total zones, 6 s 30 Recipes with advanced tungsten suspension Felt lapping: 80/36 tr / min, 3.2 kg-f (7 lb-ft) CDF, 10 total zones, 30 min Polishing: 80/81 rpm, 21.4 kPa (3.1 psi), 100 ml / min, 60 sec. Packaging: ex-situ: 80/36 rpm, 3.2 kg-f (7 lb-ft) CDF, 10 total zones, 24 sec. All top felts were 2.03 mm (80 mil) thick and finished with K7 circular grooves and a 40 mm thick Suba IV sub-felt. Table 7 summarizes the main felt properties, the tungsten removal rate and the maximum polishing temperature of the various polishing felts. Tungsten shrinkage rates are also shown in FIG. 8. The polishing felt of the present invention again exhibited a significantly higher shrinkage rate. Table 7 Felt Stoichiometry Size Porosity VR of Temp. VR of Temp. NH2 to NCO, of in W2000 maximum W * maximum (%) pores volume, (Â / min) of W2000 (Â / min) of W * (Pm) (%) (° C) (° C) 4 105 20 34 , 8% 5755 59 1876 39 I 87 20 33.0% 4231 56 1614 36 J 87 40 29.7% 3619 57 1531 33 K 87 40 39.1% 4231 53 1615 33 L 105 20 16.1% 4809 57 ND ND M 95 20 13.0% 4585 50 1621 34 15 * = advanced tungsten suspension ND = not available Temp. maximum is the maximum temperature achieved during polishing.
    [0016] Physical Properties The physical property data of the matrices demonstrate the critical range for H12MDI / TDI with polytetramethylene ether glycol cured with 4,4'-methylenebis (2-chloroaniline) at a stoichiometry of 105%. Unloaded samples were made in the laboratory with a stoichiometry ranging from about 87% to 115%. The hardness measurements were in accordance with ASTM-D2240 to measure the Shore D hardness using a Shore Si model 902 measuring tool with one D-end at 2 seconds and then again at 15 seconds. The shear storage module and the shear loss module were then measured with a twist setting at a frequency of 10 rad / sec and a temperature ramp of 3 ° C / min from -100 ° C to 150 ° C. C (ASTM D5279). The shear modulus samples had a width of 6.5 mm, a thickness of 1.26 to 2.0 mm and a spacer length of 20 mm. The test method for the average tensile modulus (ASTM-D412) was measured from 5 samples with the geometry as follows: shape of duff with a total length of 4.5 inches (11.4 cm), a total width of 0.75 inches, a neck length of 1.5 inches and a neck width of 0.25 inches. The handle separation was 2.5 inches (6.35 cm) with a nominal reference length entered in the program of 1.5 inches (3.81 cm for the neck), the crosshead speed was a speed of 20 inches / min (50.8 cm / min). The physical properties are summarized in Tables 8 and 9.
    [0017] Table 8 Sample Stoichiometry Density, g / cm3 Shore Shore G 'to G' to G "to G 'to felt D to D at 30 ° C, 40 ° C, 40 ° C, 90 ° C, 2 s 15 s MPa MPa MPa MPa M 86.7% 1,16 68 67 239 200 20.4 72.5 BB 91.8% 1.16 71 70 256 216 23.9 81.1 CC 95.3% 1.18 68 67 284 240 22.3 84.2 DD 100.5% 1.17 71 69 281 237 26.2 85.7 EE 103.0% 1.17 71 69 312 263 25.4 90.9 FF 105.2% 1 , 15 71 69 323 270 26.8 92.4 GG 108.3% 1.15 72 69 321 265 26.2 84.5 HH 110.8% 1.16 71 69 297 246 26.3 76.9 II 117 , 4% 1.17 67 66 269 215 26 60.7 3024955 17 Table 9 Exchange Stability Average Resistance Resistance Modulus Medium (psi) Modulus Middle Elastic (MPa) Expansion Module 25 % 25% Elongation Module (MPa) 100% Elongation Module 100% Elongation Module (MPa) Mean Torque (psi) (psi) Felt Traction (psi) traction (MPa) AA 86.7% 5372 37 57147 394 3905 27 4764 33 BB 91.8% 5545 38 60635 418 4115 28 4836 33 CC 95.3% 6011 41 62412 430 4282 3 0 4954 34 DD 100.5 5363 37 64914 448 4379 30 4907 34% EE 103.0 4790 33 67554 466 4450 31 4931 34% FF 105.2 4761 33 67216 464 4460 31 4927 34 ° h GG 108.3 4622 32 64893 448 4319 30 4635 32% HH 110.8 4469 31 66564 459 4343 30 4577 32 II 117.4 4430 31 61026 421 4266 29 4302 30 13 / o In summary, the specific combination of formulation, shear storage module, Shear loss and porosity modulus provides the tungsten and TEOS polishing characteristics. This polishing felt also had a significantly higher shrinkage speed in a TEOS sheet wafer polishing than the current IC1000 or VP5000 standard industrial polishing felts.
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. A polishing felt suitable for planarizing at least one of semiconductor, optical and magnetic substrates, the polishing felt comprising a cast polyurethane polymer material formed from a H12MDI / TDI prepolymer reaction with polytetramethylene ether glycol to form a isocyanate-terminated reaction product, the isocyanate-terminated reaction product having from 8.95 to 9.25 percent by weight of unreacted NCO, having a stoichiometric ratio NH2 to NCO of from 102 to 109 percent, the product of When the isocyanate-terminated reaction is cured with a curing agent of 4,4'-methylenebis (2-chloroaniline), the cast polyurethane polymer material, as measured in a non-porous state, has a shear storage modulus. from 250 to 350 MPa as measured with torsional fixation at 30 ° C and 40 ° C and a shear loss modulus, G "of 25 to 30 MPa as measured with a fixat torsion ion at 40 ° C (ASTM D5279) and the polishing felt having a porosity of 20 to 50 percent by volume and a density of 0.60 to 0.95 g / cm 3.
    [0002]
    2. Polishing felt according to claim 1, characterized in that a shear storage modulus ratio, G 'at 40 ° C shear loss modulus, G "at 40 ° C is 8 to 15.
    [0003]
    3. Polishing felt according to claim 1, characterized in that the isocyanate-terminated reaction product and 4,4'-methylenebis (2-chloroaniline) have the stoichiometric ratio NH2 to NCO of 103 to 107 percent.
    [0004]
    4. Polishing felt according to claim 1, characterized in that the polishing felt comprises pores having a mean diameter of less than 100 dam.
    [0005]
    5. Polishing felt according to claim 4, characterized in that the density is 0.7 to 0.9 g / cm3.
    [0006]
    A polishing felt suitable for planarizing at least one of semiconductor, optical and magnetic substrates, the polishing felt comprising a cast polyurethane polymer material formed from a H12MDI / TDI prepolymer reaction with polytetramethylene ether glycol forming an isocyanate-terminated reaction product, the isocyanate-terminated reaction product having from 8.95 to 9.25 percent by weight of unreacted NCO, having a stoichiometric ratio of NH2 to NCO of from 103 to 107 percent with the isocyanate-terminated reaction product being cured with a curing agent of 4,4'-methylenebis (2-chloroaniline), the cast polyurethane polymer material, as measured in a non-porous state, having a storage module shear strength, G 'of 250 to 350 MPa as measured with torsional fixation at 30 ° C and 40 ° C and a modulus of shear loss, G "of 25 to 30 MPa as measured with 40 ° torsion fixation (ASTM D5279), wherein a shear storage modulus ratio, G 'at 40 ° C to the shear loss modulus, G "at 40 ° C is 8 to 15 and the polishing felt having a porosity of 20 to 50 percent by volume and a density of 0.60 to 0.95 g / cm 3. 15
    [0007]
    The polishing felt according to claim 6, characterized in that a shear storage modulus ratio, G 'at 40 ° C to the shear loss modulus, G "at 40 ° C is 8 to 12.
    [0008]
    The polishing felt according to claim 6, characterized in that the isocyanate-terminated reaction product and 4,4'-methylenebis (2-chloroaniline) have the stoichiometric NH 2 to NCO ratio of from 10 4 to 10 6 percent.
    [0009]
    Polishing felt according to claim 6, characterized in that the polishing felt comprises pores having an average diameter of 10 to 60 μm. 25
    [0010]
    10. Polishing felt according to claim 9, characterized in that the density is 0.70 to 0.80 g / cm3.
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    同族专利:
    公开号 | 公开日
    TWI589613B|2017-07-01|
    US20160052103A1|2016-02-25|
    DE102015009512A1|2016-02-25|
    JP6625368B2|2019-12-25|
    CN105382680B|2020-02-28|
    FR3024955B1|2019-12-06|
    TW201615342A|2016-05-01|
    CN105382680A|2016-03-09|
    JP2016043479A|2016-04-04|
    US9731398B2|2017-08-15|
    KR20160023575A|2016-03-03|
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    法律状态:
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    2020-07-15| PLFP| Fee payment|Year of fee payment: 6 |
    2021-07-14| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    US14/465,934|US9731398B2|2014-08-22|2014-08-22|Polyurethane polishing pad|
    US14465934|2014-08-22|
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