KR20150026903A - Chemical mechanical polishing pad - Google Patents

Abstract

Provided is a chemical mechanical polishing pad which includes a polishing layer; a hardened layer; and includes a hot melt adhesive of combining the polishing layer and the hardened layer. Here, the polishing layer includes specific gravity of more than 0.6; a shore D hardness of 60 to 90; fracture elongation of 100 to 300%; and shows specific combination of initial hydrolysis stability and long-term hydrolysis instability.

Description

CHEMICAL MECHANICAL POLISHING PAD [0002]

The present invention relates to chemical mechanical polishing pads and methods of making and using the same. More specifically, the present invention relates to a polishing pad comprising: an abrasive layer; Hard layer; And a hot melt adhesive to bond the polishing layer to the hard layer; Wherein the abrasive layer has a specific gravity greater than 0.6; A Shore D hardness of 60 to 90; A fracture elongation of 100 to 300%; And a unique combination of initial hydrolysis stability and sustained hydrolytic instability; And wherein the polishing layer has a polishing surface adapted to polishing the substrate.

The fabrication of semiconductors typically involves a number of chemical mechanical planarization (CMP) processes. In each CMP process, the abrasive pad, such as an abrasive-containing polishing slurry or a polishing pad in combination with the abrasive-free reactive liquid, is planarized to remove the excess material or removed to remove excess material in a manner to maintain the flatness. The stacking of these layers is combined in such a way as to form an integrated circuit. Processing of such semiconductor devices continues to become increasingly complex because devices with fast operating speeds, low leakage currents and low power consumption are required. In terms of device structure, this is interpreted as a finer feature geometry and increased metallization level. This increasingly stringent device design requirement has led to the adoption of copper metallization with novel dielectric materials having lower dielectric constants. With the increased complexity of the device, poor physical properties often associated with low k and ultra-low k materials have led to increased demand for CMP consumables such as polishing pads and abrasive liquids.

In particular, low dielectric constant and ultra low dielectric constant dielectrics tend to have lower mechanical strength and poorer adhesion than conventional dielectrics, making planarization more difficult. Also, as the feature size of the integrated circuit is reduced, CMP-induced defects, such as scratching, become a more serious problem. In addition, the reduction in film thickness of the integrated circuit needs to provide acceptable topography to the wafer substrate, along with improvements in defects - such phase requirements require more rigorous flatness, dishing and corrosion specifications Demand.

Polyurethane polishing pads are the main pad chemistry used for a variety of demanding precision polishing applications. Polyurethane polishing pads are effective for polishing silicon wafers, pattern wafers, flat panel displays and magnetic storage disks. In particular, polyurethane polishing pads provide mechanical integrity and chemical resistance in most polishing operations used in the fabrication of integrated circuits. For example, polyurethane polishing pads have high strength for durability; Abrasion resistance to avoid wear problems during polishing; And stability for resistance to attack by strongly acidic and strong corrosive polishing liquids.

A class of polyurethane polishing layers is disclosed in U.S. Patent No. 8,288,448 (Kulp). An abrasive pad comprising a cast polyurethane polymer material formed from an isocyanate-terminated reaction product formed from a prepolymer polyol and a prepolymeric reaction of a polyfunctional isocyanate was disclosed by Culp. The isocyanate-terminated reaction product has an unreacted NCO of 4.5 to 8.7% by weight; The isocyanate-terminated reaction product is cured by a curing agent selected from the group consisting of a curing agent polyamine, a curing agent polyol, a curing agent, an alcohol amine, and mixtures thereof.

However, there continues to be a need for chemical and mechanical polishing pads that show that properties are adequately balanced, providing flatness while minimizing defect creation.

The present invention relates to a polishing layer having a polishing surface, a base surface and an average thickness ( T _{P - avg} ) measured in a direction perpendicular to the polishing surface from the polishing surface to the base surface, wherein the polishing layer is a cast polyurethane, (A) (i) a multifunctional isocyanate; And (ii) an isocyanate terminated prepolymer obtained by reaction of a polyether-based polyol, having an unreacted NCO of 8 to 9.5% by weight; (b) a curing agent selected from the group consisting of a curing agent polyamine, a curing agent polyol, a curing agent alcohol amine, and mixtures thereof; And optionally (c) a plurality of trace elements; The abrasive layer has a specific gravity of greater than 0.6; A Shore D hardness of 60 to 90; And a breaking elongation of 100 to 300%; The abrasive layer exhibits an initial hydrolytic stability at which the linear dimension of the abrasive layer sample changes by less than 1% after immersion in deionized water at 25 占 폚 for 24 hours; The abrasive layer exhibits long term hydrolytic instability wherein the linear dimension of the abrasive layer sample changes by at least 1.75% after immersion in deionized water for 7 days at 25 占 폚; A hard layer having an upper surface and a lower surface; A hot melt adhesive interposed between the base surface of the abrasive layer and the upper surface of the hard layer, wherein the hot melt adhesive bonds the abrasive layer to the hard layer; A pressure sensitive facing adhesive layer having a laminated surface and a platen side wherein the laminated side of the pressure sensitive facing adhesive layer is adjacent to a lower surface of the hard layer; And optionally a release liner, wherein the optional release liner is disposed on the positive side of the pressure sensitive platen adhesive layer.

The present invention relates to a polishing layer having a polishing surface, a base surface and an average thickness ( T _{P - avg} ) measured in a direction perpendicular to the polishing surface from the polishing surface to the base surface, wherein the polishing layer is a cast polyurethane, (A) (i) a multifunctional isocyanate; And (ii) an isocyanate terminated prepolymer obtained by reaction of a polyether-based polyol, having an unreacted NCO of 8 to 9.5% by weight; (b) a curing agent selected from the group consisting of a curing agent polyamine, a curing agent polyol, a curing agent alcohol amine, and mixtures thereof; And optionally (c) a plurality of trace elements; The curing agent and the isocyanate terminated prepolymer have a stoichiometric ratio of OH or NH ₂ to unreacted NCO of less than 80 to 95%; The abrasive layer has a specific gravity of greater than 0.6; A Shore D hardness of 60 to 90; And a breaking elongation of 100 to 300%; The abrasive layer exhibits an initial hydrolytic stability at which the linear dimension of the abrasive layer sample changes by less than 1% after immersion in deionized water at 25 占 폚 for 24 hours; The abrasive layer exhibits long term hydrolytic instability with linear dimensions of the abrasive layer sample varying from 1.75 to 3.5% after immersion in deionized water at 25 占 폚 for 7 days; A hard layer having an upper surface and a lower surface; A hot melt adhesive interposed between the base surface of the abrasive layer and the upper surface of the hard layer, wherein the hot melt adhesive bonds the abrasive layer to the hard layer; A pressure-sensitive platen layer having a laminated surface and a regular surface, wherein the laminated surface of the pressure-sensitive platen-facing adhesive layer is adjacent to a lower surface of the hard layer; And optionally a release liner, wherein the optional release liner is disposed on the positive side of the pressure sensitive platen adhesive layer.

The present invention relates to a polishing layer having a polishing surface, a base surface and an average thickness ( T _{P - avg} ) measured in a direction perpendicular to the polishing surface from the polishing surface to the base surface, wherein the polishing layer is a cast polyurethane, (A) (i) a multifunctional isocyanate; And (ii) an isocyanate terminated prepolymer obtained by reaction of a polyether-based polyol, having an unreacted NCO of 8 to 9.5% by weight; (b) a curing agent selected from the group consisting of a curing agent polyamine, a curing agent polyol, a curing agent alcohol amine, and mixtures thereof; And optionally (c) a plurality of trace elements; The abrasive layer has a specific gravity of greater than 0.6; A Shore D hardness of 60 to 90; And a breaking elongation of 100 to 300%; The abrasive layer exhibits an initial hydrolytic stability at which the linear dimension of the abrasive layer sample changes by less than 1% after immersion in deionized water at 25 占 폚 for 24 hours; The abrasive layer exhibits long term hydrolytic instability with linear dimensions of the abrasive layer sample varying from 1.75 to 3.5% after immersion in deionized water at 25 占 폚 for 7 days; A hard layer having an upper surface and a lower surface, wherein the hard layer is made of biaxially stretched polyethylene terephthalate; The hard layer has an average thickness of 6 to 15 mils; The hard layer exhibiting a Young's Modulus of 3,000 to 7,000 MPa; A hot melt adhesive interposed between the base surface of the abrasive layer and the upper surface of the hard layer, wherein the hot melt adhesive bonds the abrasive layer to the hard layer; A pressure-sensitive platen layer having a laminated surface and a regular surface, wherein the laminated surface of the pressure-sensitive platen-facing adhesive layer is adjacent to a lower surface of the hard layer; And optionally a release liner, wherein the optional release liner is disposed on the positive side of the pressure sensitive platen adhesive layer.

The present invention relates to a polishing layer having a polishing surface, a base surface and an average thickness ( T _{P - avg} ) measured in a direction perpendicular to the polishing surface from the polishing surface to the base surface, wherein the polishing layer is a cast polyurethane, (A) (i) a multifunctional isocyanate; And (ii) an isocyanate terminated prepolymer obtained by reaction of a polyether-based polyol and having an unreacted NCO greater than 8.7 wt% to 9 wt%; (b) a curing agent selected from the group consisting of a curing agent polyamine, a curing agent polyol, a curing agent alcohol amine, and mixtures thereof; And optionally (c) a plurality of trace elements; The abrasive layer has a specific gravity of greater than 0.6; A Shore D hardness of 60 to 90; And a breaking elongation of 100 to 300%; The abrasive layer exhibits an initial hydrolytic stability at which the linear dimension of the abrasive layer sample changes by less than 1% after immersion in deionized water at 25 占 폚 for 24 hours; The abrasive layer exhibits long term hydrolytic instability with linear dimensions of the abrasive layer sample varying from 1.75 to 3.5% after immersion in deionized water at 25 占 폚 for 7 days; A hard layer having an upper surface and a lower surface; A hot melt adhesive interposed between the base surface of the abrasive layer and the upper surface of the hard layer, wherein the hot melt adhesive bonds the abrasive layer to the hard layer; A pressure-sensitive platen layer having a laminated surface and a regular surface, wherein the laminated surface of the pressure-sensitive platen-facing adhesive layer is adjacent to a lower surface of the hard layer; Optionally a release liner, wherein the optional release liner is disposed on the positive side of the pressure sensitive platen adhesive layer; And an endpoint detection window. ≪ Desc / Clms Page number 2 >

The present invention provides a substrate selected from one or more of a magnetic substrate, an optical substrate, and a semiconductor substrate; Providing a chemical mechanical polishing pad according to the present invention; Polishing the surface of the substrate by causing dynamic contact between the polishing surface of the polishing layer and the substrate; A method of polishing a substrate, comprising conditioning the polishing surface with an abrasive conditioner.

1 is a perspective view of a chemical mechanical polishing pad of the present invention.
2 is a cross-sectional cutaway front view of the chemical mechanical polishing pad of the present invention.
3 is a top view of the chemical mechanical polishing pad of the present invention.
4 is a side perspective view of an abrasive layer of the present invention.
5 is a cross-sectional cutaway front view of the chemical mechanical polishing pad of the present invention.
6 is a front view of a plug-in place window block of the present invention.
7 is a cross-sectional cutaway front view of a chemical mechanical polishing pad of the present invention having a plug-in place window block.
8 is a cross-sectional cutaway front view of a chemical mechanical polishing pad of the present invention having a plug-in place window block.
9 is a cross-sectional cutaway front view of a chemical mechanical polishing pad of the present invention having a plug-in place window block.
10 is a cross-sectional cutaway front view of a chemical mechanical polishing pad of the present invention having an integral window.

Conventional polyurethane polishing layers have been designed using polyurethane materials that exhibit hydrolytic stability and prolonged hydrolytic stability. It is common practice to use polyurethane materials that maintain dimensional stability when immersed in water for a long period of time for use in chemical mechanical polishing layers. Applicant has surprisingly found a specific gravity of greater than 0.6; A Shore D hardness of 60 to 90; A fracture elongation of 100 to 300%; And the chemical mechanical polishing pad of the present invention having an abrasive layer that exhibits a particular combination of initial hydrolysis stability and long term hydrolytic instability provides defects that can lead to low device yields and in particular improved planarization performance while minimizing scratch defects . A particular balance of properties exhibited by the abrasive layer of the present invention enables effective planarization of semiconductor wafers with exposed copper features, for example, with minimal defect generation.

The term " average total thickness ( T _{T - avg} ) " used in connection with the chemical mechanical polishing pad 10 having the polishing surface 14 in the present application and the appended claims refers to the _distance from the polishing surface 14 to the hard layer 25 ( T _T ) of the chemical mechanical polishing pad measured in the normal direction with respect to the polishing surface 14 to the lower surface 27 of the polishing pad 14 (see FIGS. 1 , 2 , 5 and 7-10 ).

When present, and is used by the patent in connection with the polishing layer in the appended claims, the term "initial hydrolytic stability" is measured according to the procedure described for Example, the polishing layer sample at 25 ℃ after immersion in deionized water for 24 hours Means that the linear dimension of < RTI ID = 0.0 >

Herein and used in the patent in connection with the polishing layer in the appended claims, the term "hydrolytic stability over a long period of time" is polished after immersion in deionized water, while, at 25 ℃ 7 il as measured according to the procedure described for Example Means that the linear dimension of the layer sample varies by less than 1.75%.

Herein and used in the patent in connection with the polishing layer in the appended claims, the term "long-term hydrolytic instability (sustained hidrolytic instability) "is meant to change in 25 ℃ as above after immersion in deionized water and the linear dimension of the abrasive layer sample of 1.75% in 7 days when measured according to the procedure described for Example.

The term " substantially circular cross section " as used herein in connection with the chemical mechanical polishing pad 10 in this application and the appended claims refers to the distance from the central axis 12 of the polishing surface 14 of the polishing layer 20 to the outer periphery 15 Means that the longest radius r of the cross section from the center axis 12 of the polishing surface 14 to the outer periphery 15 is 20% or more shorter than the shortest radius r of the cross section of the cross section from the central axis 12 to the outer periphery 15 (see Fig. 1 ) .

The chemical mechanical polishing pad 10 of the present invention is preferably adapted to rotate about the central axis 12 (see FIG. 1 ). Preferably, the polishing surface 14 of the polishing layer 20 is a plane 28 perpendicular to the central axis 12 . The rotation of the chemical mechanical polishing pad 10 is preferably in the center 85 to 95 ° with respect to the shaft 12, preferably a central axis plane (28) at an angle (γ) of 90 ° with respect to 12 Lt; / RTI > Preferably, the polishing layer 20 has a polishing surface 14 that is substantially perpendicular to the central axis 12 and has a substantially circular cross-section. Preferably, the radius r of the cross-section of the polishing surface 14 perpendicular to the central axis 12 is less than 20% in the cross-section, more preferably less than 10% in the cross-section.

The chemical mechanical polishing pad 10 of the present invention is specifically designed to facilitate polishing of a substrate selected from one or more of a magnetic substrate, an optical substrate, and a semiconductor substrate. Preferably, the chemical mechanical polishing pad 10 of the present invention is designed to facilitate polishing of semiconductor substrates. More preferably, the chemical mechanical polishing pad 10 of the present invention is designed to facilitate polishing of exposed copper features on a semiconductor wafer substrate surface.

The chemical mechanical polishing pad 10 of the present invention, the polishing surface 14, base surface 17 and the grinding surface (14) from the base surface (17) with respect to the grinding surface 14 to the mean thickness measured in the vertical direction ( abrasive layer 20 having _{avg) -} T _P; A hard layer 25 having an upper surface 26 and a lower surface 27 ; Base surface 17 and the hot-melt adhesive (23) interposed between the upper surface 26 of the rigid layer (25) wherein a hot-melt adhesive 23 of the polishing layer 20 has a polishing layer 20, the hard layer (25 ); Optionally a pressure-sensitive platen adhesive layer 70 is preferably - wherein the pressure-sensitive platen adhesive layer 70 is disposed on when 27 of the hard layer (25)] (, an optional pressure sensitive platen adhesive layer is chemical-mechanical Facilitating fixation of the polishing pad to the polishing machine); Optionally a release liner 75 wherein the pressure sensitive platen adhesive layer 70 is interposed between the lower surface 27 of the hard layer 25 and an optional release liner 75 ; And optionally an endpoint detection window 30 (preferably, the endpoint detection window facilitates in situ polishing endpoint detection); Wherein the abrasive layer ( 20 ) is cast polyurethane and the cast polyurethane comprises (a) (i) a multifunctional isocyanate; (Preferably from 8.65 to 9.05% by weight, more preferably from 8.7 to 9% by weight) of unreacted NCO obtained by the reaction of the polyether-based polyol and (ii) An isocyanate terminated prepolymer; (b) a curing agent selected from the group consisting of a curing agent polyamine, a curing agent polyol, a curing agent alcohol amine, and mixtures thereof; And (c) optionally a reaction product of components comprising a plurality of trace elements; The abrasive layer 20 has a specific gravity of greater than 0.6; Shore D hardness of from 60 to 90 (preferably greater than 60 to 75; more preferably 61 to 75; most preferably greater than 65 to 70); And 100 to 300% (preferably 100 to 200%; more preferably 125 to 175%; most preferably 150 to 160%) of the elongation at break; The abrasive layer 20 exhibits an initial hydrolytic stability (measured according to the method described in the Examples ) wherein the linear dimension of the abrasive layer sample after immersion in deionized water at 25 占 폚 for 24 hours varies by less than 1%; The abrasive layer 20 has a linear dimension of at least 1.75% (preferably 1.75 to 5%; more preferably 1.75 to 3.5%; most preferably, (Measured by the method described in the Examples ) (see Figs. 1-10 ).

Preferably, the multifunctional isocyanate used to form the abrasive layer 20 is selected from the group consisting of aliphatic polyfunctional isocyanates, aromatic polyfunctional isocyanates, and mixtures thereof. Preferably, the multifunctional isocyanate used in the formation of the abrasive layer 20 contains two reactive isocyanate groups (i.e., NCO). More preferably, the multifunctional isocyanate used in the formation of the abrasive layer 20 is 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 4,4'-diphenylmethane diisocyanate; Naphthalene-1,5-diisocyanate; Tolidine diisocyanate; para-phenylene diisocyanate; Xylylene diisocyanate; Isophorone diisocyanate; Hexamethylene diisocyanate; 4,4'-dicyclohexylmethane diisocyanate; Cyclohexane diisocyanate; ≪ / RTI > and mixtures thereof. Most preferably, the multifunctional isocyanate used in the formation of the abrasive layer 20 is selected from the group consisting of toluene diisocyanate (preferably 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof) Selected toluene diisocyanate).

Preferably, the isocyanate terminated prepolymer used in the formation of the abrasive layer 20 has 8 to 9.5% by weight of unreacted isocyanate (NCO) groups. More preferably, the isocyanate terminated prepolymer used in the formation of the abrasive layer 20 has 8.65 to 9.05 wt% (most preferably, greater than 8.7 wt% to 9 wt%) unreacted isocyanate (NCO) groups.

Preferably, the polyether-based polyol is a polypropylene glycol-based polyol and is present in an amount of from 8 to 9.5 wt% (more preferably from 8.65 to 9.05 wt%; most preferably from greater than 8.7 wt% to 9 wt%) of unreacted And has an isocyanate (NCO) concentration. Examples of commercially available polypropylene glycol based isocyanate terminated urethane prepolymers are available from the Imuthane prepolymer (available from COIM USA, Inc., such as PPT-80A, PPT-90A, PPT-95A, PPT-65D, PPT-75D); Adiprene 占 prepolymer (available from Chemtura, such as LFG 963A, LFG 964A, LFG 740D); And the Andur® prepolymer (available from the Anderson Development Company, such as 8000APLF, 9500APLF, 6500DPLF, 7501DPLF).

Preferably, the isocyanate terminated prepolymer used in the formation of the abrasive layer 20 comprises less than 0.1 wt% free toluene diisocyanate (TDI) Is an isocyanate terminated urethane prepolymer having a low degree of freedom having a monomer content.

Preferably, the curing agent used to form the polishing layer 20 is selected from the group consisting of polyamines, curing agent polyols, curing agent alcohol amines, and mixtures thereof. More preferably, the curing agent used to form the polishing layer 20 is selected from polyols and polyamines. Even more preferably, the curing agent used to form the polishing layer 20 is a bifunctional curing agent selected from the group consisting of primary amines and secondary amines. More preferably, the bifunctional curing agent is diethyltoluenediamine (DETDA); 3,5-dimethylthio-2,4-toluenediamine and its isomers; 3,5-diethyltoluene-2,4-diamine and its isomers (for example, 3,5-diethyltoluene-2,6-diamine); 4,4'-bis- (sec-butylamino) -diphenylmethane; 1,4-bis- (sec-butylamino) -benzene; 4,4'-methylene-bis- (2-chloroaniline); 4,4'-methylene-bis- (3-chloro-2,6-diethylaniline) (MCDEA); Polytetramethylene oxide-di-p-aminobenzoate; N, N'-dialkyldiaminodiphenylmethane; p, p'-methylene dianiline (MDA); m-phenylenediamine (MPDA); 4,4'-methylene-bis- (2-chloroaniline) (MBOCA); 4,4'-methylene-bis- (2,6-diethylaniline) (MDEA); 4,4'-methylene-bis- (2,3-dichloroaniline) (MDCA); 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 2,2 ', 3,3'-tetrachlorodiaminodiphenylmethane; Trimethylene glycol di-p-aminobenzoate; Isomers thereof; And mixtures thereof. Most preferably, the curing agent is 4,4'-methylene-bis- (2-chloroaniline) (MBOCA).

Preferably, the stoichiometric ratio of the reactive hydrogen groups of the curing agent (i.e., the sum of amine (NH ₂ ) and hydroxyl (OH) groups) to the unreacted isocyanate (NCO) group of the isocyanate terminated prepolymer is less than 80 to 95% , More preferably from 85 to less than 95%, even more preferably from 87 to 94%, most preferably from 89 to 92%).

The polishing layer 20 optionally further comprises a plurality of trace elements. Preferably, a plurality of trace elements are uniformly dispersed throughout the polishing layer 20 . Preferably, the plurality of trace elements is selected from entrapped bubbles, hollow core polymer material, liquid filled hollow core polymer material, water soluble material, insoluble phase material (e.g., mineral oil), and combinations thereof. More preferably, a plurality of trace elements are selected from trapped bubbles and hollow core polymer materials that are uniformly distributed throughout the polishing layer 20 . Preferably, the majority of trace elements have a weight average diameter of less than 150 microns (more preferably less than 50 microns, most preferably 10 to 50 microns). Preferably, the plurality of trace elements include polymeric microspheres having an outer wall of a polyacrylonitrile or polyacrylonitrile copolymer (e.g., Expancel < (R) > manufactured by Akzo Nobel) . Preferably, the majority of trace elements are incorporated into the polishing layer 20 with a porosity of 0 to 35 vol% (more preferably 10 to 25 vol% porosity).

The abrasive layer 20 may be provided in a porous and non-porous (i.e., non-filled) structure. Preferably, the abrasive layer 20 has a specific gravity of greater than 0.6 as measured according to ASTM D1622. More preferably, the abrasive layer 20 has a specific gravity of from 0.6 to 1.5 (even more preferably from 0.7 to 1.2, most preferably from 0.95 to 1.2) as measured according to ASTM D1622.

Preferably, the abrasive layer 20 exhibits a Shore D hardness of 60 to 90, as measured according to ASTM D2240. More preferably, the abrasive layer 20 exhibits a Shore D hardness of greater than 60 to 75 (more preferably 61 to 75; most preferably, greater than 65 to 70) as measured according to ASTM D2240.

Preferably, the abrasive layer 20 exhibits a fracture elongation of 100 to 300% as measured according to ASTM D412. Preferably, the abrasive layer 20 exhibits a fracture elongation of 100 to 200% (even more preferably 125 to 175%, most preferably 150 to 160%) as measured according to ASTM D412.

Those skilled in the art will appreciate the choice of polishing layer 20 having a thickness ( T _P ) suitable for use in a chemical mechanical polishing pad 10 for a given polishing operation. Preferably, the polishing layer 20 exhibits an average thickness ( T _{P - avg} ) along an axis A perpendicular to the plane 28 of the polishing surface 14 . Is (2, 5, and 7 - Reference 10); _{- (avg} T _P) are (most preferably 70 to 90 mil preferably 30 to 130 mil than) 20 to 150 mil and more preferably, the average thickness .

Preferably, the polishing surface 14 of the polishing layer 20 is a substrate (more preferably a semiconductor substrate, even more preferably a semiconductor wafer, most preferably a substrate) selected from at least one of a magnetic substrate, Is adapted to the polishing of a semiconductor wafer having a surface with exposed copper features. The polishing surface 14 of the polishing layer 20 represents one or more of macrotexture and microtexture that facilitate polishing of the substrate. Preferably, the abrasive surface 14 represents a macrotexture, wherein the macrotexture comprises (i) relieving the hydration phenomenon; (ii) affecting the polishing medium flow; (iii) varying the stiffness of the abrasive layer; (iv) reducing the edge effect; And (v) facilitating transfer from the area between the polishing surface 14 of the abrasive debris and the substrate being abraded.

The abrasive surface 14 preferably exhibits a macrotexture selected from one or more of a perforation and a groove. Preferably, the perforations may extend partially or completely along the thickness of the abrasive layer 20 from the abrasive surface 14 . Preferably, the grooves are arranged on the polishing surface 14 such that one or more grooves slip over the substrate as the pad 10 rotates during polishing. Preferably, the grooves are selected from curved grooves, linear grooves, and combinations thereof. The groove represents a depth of 10 mils or more (preferably 10 to 120 mils). Preferably, the groove has a depth selected from at least 10 mils, at least 15 mils and from 15 to 120 mils; A width selected from more than 10 mils and 10 to 100 mils; And a pitch of at least 30 mils, more than 50 mils, 50 to 200 mils, 70 to 200 mils, and 90 to 200 mils.

Preferably, the polishing layer 20 contains less than 1 ppm of abrasive particles incorporated therein.

Preferably, the hard layer 25 is made of a material selected from the group consisting of polymers, metals, reinforcing polymers, and combinations thereof. More preferably, the hard layer 25 is made of a polymer. Most preferably, the rigid layer 25 is made of polyester, nylon, epoxy, fiberglass reinforced epoxy; (More preferably, a polyester, more preferably a polyethylene terephthalate polyester, and most preferably a biaxially stretched polyethylene terephthalate polyester) selected from the group consisting of a polycarbonate and a polycarbonate.

Preferably, the hard layer 25 has an average thickness ( T _{R - avg} ) of more than 5 to 60 mils (more preferably 6 to 15 mils, most preferably 6 to 8 mils).

Preferably, both the upper surface 26 and the lower surface 27 of the rigid layer 25 have no grooves. More preferably, the upper surface 26 and the lower surface 27 are both active surfaces. Most preferably, the top surface 26 and the bottom surface 27 have a thickness of 1 to 500 nm (preferably 1 to 100 nm; more preferably 10 to 50 nm; most preferably, ( Ra ) of 20 to 40 nm).

Preferably, the upper surface 26 of the rigid layer 25 has adhesive strength is improved treatment agent to improve the adhesion between the hard layer 25 and the reactive hot-melt adhesive (23). Those skilled in the art will know how to select the appropriate adhesion promoting agent in view of the composition of the hard layer 25 and the composition of the hot melt adhesive 23 .

Preferably, the hard layer 25 has a hardness of at least 100 MPa (more preferably 1,000 to 10,000 MPa; even more preferably 2,500 to 7,500 MPa; most preferably 3,000 to 10,000 MPa, 7,000 MPa).

Preferably, the hard layer 25 exhibits a porosity of less than 0.1% by volume (more preferably less than 0.01% by volume).

Preferably, the hard layer 25 has an average thickness of 6 to 15 mils; And a biaxially stretched polyethylene terephthalate having a Young's modulus measured according to ASTM D882-12 of 2,500 to 7,500 MPa (most preferably 3,000 to 7,000 MPa).

Those skilled in the art will know how to select a hot melt adhesive 23 suitable for use in the chemical mechanical polishing pad 10 . Preferably, the hot melt adhesive 23 is a cured reactive hot melt adhesive. More preferably, the hot-melt adhesive 23 exhibits a melting temperature of from 50 to 150 ° C, preferably from 115 to 135 ° C in its uncured state and exhibits a pot life of 90 minutes or less after melting, It is a cured reactive hot melt adhesive. Most preferably, the hot melt adhesive 23 comprises a polyurethane resin (for example Mor-Melt R5003 available from Rohm and Haas) in its uncured state.

The chemical mechanical polishing pad 10 is preferably adapted to be interfaced with the polishing platen. Preferably, the chemical mechanical polishing pad 10 is adapted to adhere to the abrasive platen. The chemical mechanical polishing pad 10 may be attached to a platen using one or more of a pressure sensitive adhesive and a vacuum.

Preferably, the chemical mechanical polishing pad 10 comprises a pressure sensitive platen adhesive layer 70 applied to the lower surface 27 of the hard layer 25 . Those skilled in the art will know how to choose a pressure sensitive adhesive suitable for use as the pressure sensitive platen layer 70 . Preferably, the chemical mechanical polishing pad 10 also will include a release liner 75 applied over the pressure sensitive platen adhesive layer 70, wherein the pressure sensitive platen adhesive layer 70 when the hard layer (25) It is interposed between 27 and release liner 75 (Figs. 2 and 7 - reference 10).

An important step in the substrate polishing operation is to determine the end point of the process. One popular method of in situ detection of an endpoint involves providing a window to the polishing pad that is transmissive to a selected wavelength of light. During polishing, a light beam is directed through the window to the wafer surface and the wafer surface reflects the light back through the window and into a detector (e.g., a spectrophotometer). Based on the return signal, the nature of the substrate surface (e.g., film thickness on the surface) for endpoint detection can be determined. To facilitate this light based endpoint method, the chemical mechanical polishing pad 10 of the present invention optionally further comprises an endpoint detection window 30 . Preferably, the endpoint detection window comprises an integral window 34 incorporated into the polishing layer 20 ; And a plug-in place window block 32 incorporated in the chemical mechanical polishing pad 10 (see FIG. 1-10 ). Those skilled in the art will know how to select endpoint detection windowing materials suitable for use in an intended polishing process.

Preferably, the endpoint detection window used in the chemical mechanical polishing pad 10 of the present invention is an integral window 34 incorporated into the polishing layer 20 . Preferably, the integration window 34 is a chemical mechanical polishing pad (10) containing the grinding surface 14, base surface 17 and the grinding surface of the abrasive surface (14) from (14) to the base surface (17) An abrasive layer ( 20 ) having an average thickness ( T _{P - avg} ) measured in the vertical direction with respect to the abrasive layer ( 20 ); A hard layer 25 having an upper surface 26 and a lower surface 27 ; Base surface 17 and the hot-melt adhesive (23) interposed between the upper surface 26 of the rigid layer (25) wherein a hot-melt adhesive 23 of the polishing layer 20 has a polishing layer 20, the hard layer (25 ); A pressure-sensitive platen base adhesive 70 ; A release liner 75 wherein the pressure sensitive platen adhesive 70 is interposed between the lower surface 27 of the hard layer 25 and the release liner 75 ; And an integral window ( 34 ) immersed in the polishing layer ( 20 ); Wherein the abrasive layer ( 20 ) is cast polyurethane and the cast polyurethane comprises (a) (i) a multifunctional isocyanate; And (ii) from 8 to 9.5 wt% (more preferably from 8.65 to 9.05 wt%; most preferably from greater than 8.7 wt% to 9 wt%) of unreacted NCO An isocyanate terminated prepolymer having an isocyanate terminated prepolymer; (b) a curing agent selected from the group consisting of a curing agent polyamine, a curing agent polyol, a curing agent alcohol amine, and mixtures thereof; And (c) optionally a reaction product of components comprising a plurality of trace elements; The abrasive layer 20 has a specific gravity of greater than 0.6; Shore D hardness of from 60 to 90 (preferably greater than 60 to 75; more preferably 61 to 75; most preferably greater than 65 to 70); And 100 to 300% (preferably 100 to 200%; more preferably 125 to 175%; most preferably 150 to 160%) of the elongation at break; The abrasive layer 20 exhibits an initial hydrolytic stability (measured according to the method described in the Examples ) wherein the linear dimension of the abrasive layer sample after immersion in deionized water at 25 占 폚 for 24 hours varies by less than 1%; The abrasive layer 20 (Preferably 1.75 to 5%; more preferably 1.75 to 3.5%; most preferably 2 to 3%) of the abrasive layer sample after immersion in deionized water for 7 days at < RTI ID = 0.0 & ) Exhibiting varying long term hydrolytic instability (measured according to the methods described in the Examples ); The polishing layer 20 has a polishing surface 14 adapted to polishing the substrate. The integral window 34 preferably has a thickness T _W measured along an axis B perpendicular to the plane 28 of the polishing surface 14 (see FIG. 10 ). Preferably, the one-piece window 34 is the polishing surface 25 of the plane 28, the vertical axis (B) Therefore, the average thickness with respect to _- have the (T _{W avg),} where the average window thickness (T _{W - avg} Is equal to the average thickness ( T _{P - avg} ) of the polishing layer 20 (see FIG. 10 ).

Preferably, the endpoint detection window used in the chemical mechanical polishing pad 10 of the present invention is a plug-in place window block 32 . Preferably, the chemical mechanical polishing pad 10 containing the plug-in place window block 32 comprises a polishing surface 14 , a base surface 17 and a polishing surface 14 from the polishing surface 14 to the base surface 17 An abrasive layer ( 20 ) having an average thickness ( T _{P - avg} ) measured in a direction perpendicular to the _substrate ( 14 ); A hard layer 25 having an upper surface 26 and a lower surface 27 ; Base surface 17 and the hot-melt adhesive (23) interposed between the upper surface 26 of the rigid layer (25) wherein a hot-melt adhesive 23 of the polishing layer 20 has a polishing layer 20, the hard layer (25 ); A pressure-sensitive platen base adhesive 70 ; A release liner 75 wherein the pressure sensitive platen adhesive 70 is interposed between the lower surface 27 of the hard layer 25 and the release liner 75 ; And a plug-in place window ( 32 ) immersed in the chemical mechanical polishing pad ( 10 ); Wherein the abrasive layer ( 20 ) is cast polyurethane and the cast polyurethane comprises (a) (i) a multifunctional isocyanate; And (ii) an unreacted NCO obtained by the reaction of a polyether-based polyol and having 8 to 9.5 wt% (preferably, 8.65 to 9.05 wt%; more preferably, greater than 8.7 wt% to 9.00 wt% An isocyanate terminated prepolymer; (b) a curing agent selected from the group consisting of a curing agent polyamine, a curing agent polyol, a curing agent alcohol amine, and mixtures thereof; And (c) optionally, a reaction product of components comprising a plurality of trace elements; The abrasive layer 20 has a specific gravity of greater than 0.6; Shore D hardness of from 60 to 90 (preferably greater than 60 to 75; more preferably 61 to 75; most preferably greater than 65 to 70); And 100 to 300% (preferably 100 to 200%; more preferably 125 to 175%; most preferably, 150 to 160%) elongation elongation; The abrasive layer 20 exhibits an initial hydrolytic stability (measured according to the method described in the Examples ) wherein the linear dimension of the abrasive layer sample after immersion in deionized water at 25 占 폚 for 24 hours varies by less than 1%; The abrasive layer 20 has a linear dimension of at least 1.75% (preferably 1.75 to 5%; more preferably 1.75 to 3.5%; most preferably, (2 to 3% as determined by the method described in the Examples) and exhibiting varying organoleptic hydrolytic instability (measured according to the methods described in the Examples ); The polishing layer ( 20 ) has a polishing surface ( 14 ) adapted to polishing the substrate; The chemical mechanical polishing pad 10 has a through opening 35 extending through the chemical mechanical polishing pad 10 from the polishing surface 14 of the polishing layer 20 to the bottom surface 27 of the hard layer 25 ; The plug-in place window block 30 is disposed within the through opening 35 ; The plug-in place window block 30 is fixed to the pressure sensitive platen adhesive 70 . The plug-in place window block 30 has a thickness T _W measured along an axis B perpendicular to the plane 28 of the polishing surface 14 (see FIGS . 5-7 ). Preferably, plug-in-place window block 30, the average window thickness along a perpendicular axis (B) with respect to the plane 28 of the polishing surface ₍₂₅₎ have a (T _{W avg),} where the average window thickness ( T _{W - avg} ) is the average overall thickness ( T _{T - avg} ) of the chemical mechanical polishing pad 10 from 5 mils (see FIG. 7 ). More preferably, the plug-in place window block 30 has an average window thickness ( T _{W -avg} ) of less than 5 millimeters to less than T _{T - avg} . Still more preferably, a plug-in-place window block 30 (more preferably, 15 to 50 mil more; most preferably 20 to 40 mils) mil 5 mil to 75 average window thickness (T _{W - avg} ) (See Figs. 5-7 ).

Preferably, the endpoint detection window used in the chemical mechanical polishing pad 10 of the present invention is a plug-in place window block 32 . Preferably, the polishing surface to the plug-in-place window chemical mechanical polishing pad 10 containing the block 32 is the polishing surface 14, base surface 17, a polishing surface 14 from the base surface 17 ( counter to extend the through-passage 35 extending through the thickness (T _P) of the abrasive layer 20 and the polishing layer 20 having _{avg) -} the average thickness (T _P measured in a direction perpendicular to 14) at the interface between including a bore (counterbore) opening 40, wherein the counterbore opening 40 is open on the grinding surface 14 counterbore opening 40 and the through-passage (35), the axis (a) and to form; (ledge 45) (see FIGS. 1, 4, 6 and 8) parallel to and along the axis (B) perpendicular to the plane 28 of the polishing surface 14 of the ledge depth (D _O). Preferably, the ledge 45 is parallel to the polishing surface 14 . Preferably, the counterbore opening defines a cylindrical volume with an axis parallel to the axis A. Preferably, the counterbore openings define a non-cylindrical volume. Preferably, the plug-in place window block 32 is disposed within the counterbore opening 40 . Preferably, the plug-in place window block 32 is disposed within the counterbore opening 40 and is attached to the polishing layer 20 . Preferably, the plug-in place window block 32 is attached to the polishing layer 20 using at least one of ultrasonic welding and adhesive. Preferably, the average depth ( D _{O - avg} ) of the counterbore openings along the axis B parallel to the axis A and perpendicular to the plane 28 of the polishing surface 14 is between 5 and 75 millimeters (Preferably 10 to 60 mils, more preferably 15 to 50 mils, most preferably 20 to 40 mils). Preferably, the average depth ( D _{O - avg} ) of the counterbore openings is less than or equal to the average thickness ( T _{W - avg} ) of the plug-in place window block 32 (see Figures 6 and 8 ). More preferably, the average depth ( D _{O - avg} ) of the counterbore openings satisfies the following relationship.

0.90 * T _{W - avg} D _{O - avg} T _{W - avg}

More preferably, the average depth ( D _{O - avg} ) of the counterbore openings satisfies the following relationship.

0.95 * T _{W - avg} D _{O - avg} < T _{W - avg}

Preferably, the endpoint detection window used in the chemical mechanical polishing pad 10 of the present invention is a plug-in place window block 32 . Preferably, the polishing surface to the plug-in-place window chemical mechanical polishing pad 10 containing the block 32 is the polishing surface 14, base surface 17, a polishing surface 14 from the base surface 17 ( an abrasive layer (20), and a chemical mechanical through-passage 35 extending through the entire thickness (T _T) of the polishing pad 10 having an _{avg) -} 14), the average thickness (T _P measured in a direction perpendicular to the comprising, wherein the polishing layer opening 37 is open on the grinding surface 14 on the upper surface 26 of the hard layer 25, the polishing layer openings 37 and the through-passage to the polishing layer opening 37 to extend ( to form 55,; 35), the shelf (shelf of the plane 28, the depth (D _O) along a perpendicular axis (B) with respect to at the interface, the axis (a) and parallel to the polishing surface 14 between 1, 4, 6 and 9 ). Preferably, the shelf 55 is parallel to the polishing surface 14 . Preferably, the abrasive layer opening 37 defines a cylindrical volume with an axis parallel to the axis A. Preferably, the abrasive layer opening 37 defines a non-cylindrical volume. Preferably, the plug-in place window block 32 is disposed within the polishing layer opening 37 . Preferably, the plug-in place window block 32 is disposed in the polishing layer opening 37 and attached to the upper surface 26 of the hard layer 25 . Preferably, the plug-in place window block 32 is attached to the upper surface 26 of the hard layer 25 using at least one of ultrasonic welding and adhesive. Preferably, the average depth ( D _{O - avg} ) of the counterbore openings along the axis B parallel to the axis A and perpendicular to the plane 28 of the polishing surface 14 is between 5 and 75 millimeters (Preferably 10 to 60 mils, more preferably 15 to 50 mils, most preferably 20 to 40 mils). Preferably, the average depth ( D _{O - avg} ) of the counterbore openings is less than or equal to the average thickness ( T _{W - avg} ) of the plug-in place window block 32 (see Figures 6 and 9 ). More preferably, the average depth ( D _{O - avg} ) of the counterbore openings satisfies the following relationship.

0.90 * T _{W - avg} D _{O - avg} T _{W - avg}

More preferably, the average depth ( D _{O - avg} ) of the counterbore openings satisfies the following relationship.

0.95 * T _{W - avg} D _{O - avg} < T _{W - avg}

Some embodiments of the present invention will now be described in detail in the following examples .

Example  One: Of the abrasive layer  Produce

A cast polyurethane cake was prepared by mixing (a) an isocyanate termination reserve at 51 DEG C obtained by the reaction of a polyfunctional isocyanate (i.e., toluene diisocyanate) with a polyether-based polyol (i.e. Adiprene® LFG740D available from Kemtura Corporation) polymer; (b) a curing agent at 116 占 폚 (i.e., 4,4'-methylene-bis- (2-chloroaniline)); And (c) 0.3% by weight of trace elements (i. E., 551 DE40d42Excelcel microspheres available from Akzo Nobel). The ratio of the isocyanate terminated prepolymer to the curing agent is such that the stoichiometry defined as the ratio of the active hydrogen group of the curing agent (i.e., the sum of the -OH group and the -NH ₂ group) to the unreacted isocyanate (NCO) group of the isocyanate terminated prepolymer is 91 %. A number of trace elements were mixed with an isocyanate terminated prepolymer prior to addition of the curing agent. Thereafter, the isocyanate terminated prepolymers incorporating a large number of trace elements and curing agents were mixed together using a high shear mixing head. After being discharged from the mixing head, the combination was dispensed over a period of 5 minutes into a circular mold having a diameter of 86.4 cm (34 inches) to provide a total pour thickness of approximately 8 cm (3 inches). After the dispensed combination was gelled for 15 minutes, the mold was placed in a curing oven. The mold was then cured in a curing oven using the following cycle: oven set temperature of 30 minutes gradient from ambient temperature to 104 캜, followed by 15.5 hours at an oven set temperature of 104 캜, then from 104 캜 to 21 캜 Oven setting temperature of 2 hour gradient.

Subsequently, the cured polyurethane cake was removed from the mold and skived with a plurality of abrasive layers having an average thickness ( T _{P - avg} ) of 2.0 mm (80 mils) at a temperature of 30 to 80 ° C Cutting with a rotating blade). The skiving process was started from the top of each cake.

Abrasive layer  Analysis of properties

The abrasive layer material having no grooves prepared according to Example 1 was analyzed and the physical properties reported in Table 1 were measured. The reported specific gravity was measured in comparison with pure water according to ASTM D1622; Note that the reported Shore D hardness is measured in accordance with ASTM D2240.

The tensile properties of the abrasive layer (i.e., median tensile strength, median elongation at break, median modulus, toughness) were measured using an Alliance RT / 5 mechanical tester, available from MTS Systems Corporation, according to ASTM D412 And measured at a crosshead speed of 50.8 cm / min. All tests were performed in a temperature and humidity controlled laboratory set at 23 &lt; 0 &gt; C and 50% relative humidity. After all the test samples were conditioned for 5 days under the mentioned laboratory conditions, the tests were performed. The reported tensile strength median (MPa) and fracture elongation median (%) of the abrasive layer material were determined from the stress-strain curves of the five replicate samples.

The storage modulus (G ') and loss modulus (G ") of the abrasive layer materials were measured using a TA Instruments ARES Rheometer with a torsion fastener according to ASTM D5279-08. The linear viscoelastic response of the sample was measured at a test frequency of 10 rad / s (1.59 Hz) and at a temperature gradient of 3 DEG C / min from -100 DEG C to 200 DEG C. The test sample Was stamped from the abrasive layer using a 47.5 mm x 7 mm die on an Indusco hydraulic swing arm cutter and then cut to length of approximately 35 mm using scissors.

Analysis of Hydrolysis Stability

Next, the abrasive layer material having no grooves prepared according to Example 1 was analyzed to determine whether the material exhibited initial hydrolysis stability and organ hydrolysis instability. Three commercially available abrasive layer materials were also analyzed (i. E., IC1000 ™ abrasive layer material available from Rohm and Haas Electronic Materials, Inc., Cincinnati, Ohio; VisionPad ™ 3100 abrasive layer material and VisionPad ™ abrasive layer material). Commercial pad specifications for commercially available abrasive layer materials are provided in Table 2 . Specifically, a 1.5 "x 1.5" sample of each 2 mm thick abrasive layer material was initially measured along both dimensions (ie, x and y dimensions) of 1.5 "using a caliper. was immersed in the deionized water of 25 ℃. after the sample was immersed for 24 hours and 7 days of immersion, it was again measured along the x and y dimensions using calipers. the results of the measurements are given in Table 3.

Claims (10)

An abrasive layer having an average thickness ( T _P-avg ) measured in a direction perpendicular to the polishing surface from the polishing surface, the base surface and the polishing surface to the base surface;
A hard layer having an upper surface and a lower surface;
A hot melt adhesive interposed between the base surface of the abrasive layer and the upper surface of the hard layer and bonding the abrasive layer to the hard layer;
A pressure sensitive platen layer having a laminate surface and a platen side, the laminate surface of the pressure-sensitive platen adhesive layer being adjacent to a lower surface of the hard layer; And
Optionally, the release liner disposed on the positive side of the pressure-
Lt; / RTI &gt;
Here, the abrasive layer is a cast polyurethane, and the cast polyurethane
(a) (i) a multifunctional isocyanate; And
(ii) a polyether-based polyol
An isocyanate terminated prepolymer obtained by reaction of 8 to 9.5% by weight of unreacted NCO;
(b) a curing agent selected from the group consisting of a curing agent polyamine, a curing agent polyol, a curing agent alcohol amine, and mixtures thereof; And
Optionally (c) a plurality of trace elements
The reaction product of the components comprising;
The abrasive layer has a specific gravity of greater than 0.6; A Shore D hardness of 60 to 90; And a breaking elongation of 100 to 300%;
The abrasive layer exhibits an initial hydrolytic stability at which the linear dimension of the abrasive layer sample changes by less than 1% after immersion in deionized water at 25 占 폚 for 24 hours;
Wherein the abrasive layer exhibits sustained hydrolytic instability with linear dimensions of the abrasive layer sample varying by greater than or equal to 1.75% after immersion in deionized water for 7 days at &lt; RTI ID = 0.0 &gt; 25 C. &lt; / RTI &gt; The chemical mechanical polishing pad of claim 1, wherein the curing agent and the isocyanate terminated prepolymer have a stoichiometric ratio of OH or NH ₂ to unreacted NCO of less than 80 to 95%. The chemical mechanical polishing pad of claim 1, wherein the upper and lower surfaces of the hard layer are ungrooved. The chemical mechanical polishing pad of claim 1, wherein the hard layer has a Young's Modulus of 2,500 to 7,500 MPa. 3. The method of claim 2, wherein the hard layer is made of biaxially stretched polyethylene terephthalate; The hard layer has an average thickness of 6 to 15 mils; Wherein the hard layer exhibits a Young's modulus of from 3,000 to 7,000 MPa. 6. The composition of claim 5, wherein the cast polyurethane comprises: (a) (i) a multifunctional isocyanate; And (ii) a polyether-based polyol; An isocyanate terminated prepolymer having greater than 8.7 wt% to 9 wt% unreacted NCO; (b) a curing agent which is a curing agent polyamine; And (c) a reaction product of components comprising a plurality of trace elements; The specific gravity of the abrasive layer exceeding 0.6; A Shore D hardness of 61 to 75; And a fracture elongation of 100 to 200%. 7. The chemical mechanical polishing pad of claim 6, further comprising an endpoint detection window. The chemical mechanical polishing pad according to claim 7, wherein the end point detection window is an integral window. 8. The chemical mechanical polishing pad of claim 7, wherein the endpoint detection window is a plug in place window. Providing a substrate selected from one or more of a magnetic substrate, an optical substrate, and a semiconductor substrate;
Providing a chemical mechanical polishing pad according to claim 1;
Polishing the surface of the substrate by causing dynamic contact between the polishing surface of the polishing layer and the substrate;
Conditioning the abrasive surface with an abrasive conditioner
And polishing the substrate.

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