Patent Application
20100167514
The present invention relates to methods of forming integrated circuits (ICs) including MOS transistors, and more particularly to methods of forming ICs including metal gate comprising MOS transistors.
The gate electrode stack has historically been manufactured from polysilicon on silicon dioxide or nitrided silicon oxide (SiON). Recently, polysilicon has been replaced with metal and then silicon dioxide or SiON gate dielectric has been replaced with a high-k material to improve transistor performance. For example, the metal gate electrode being a good electrical conductor suppresses the gate depletion layer of a MOS transistor. This arrangement changes the gate electrode/gate dielectric interface to metal on a high-k dielectric.
To further complicate the situation, to optimize performance, different metal comprising gate materials are generally needed to provide a different work function for the NMOS devices versus the PMOS devices (generally referred to as a dual work function metal gate). In some gate stack arrangements for the dual work function metal gate, one of the metal comprising gate electrode layers (e.g. for PMOS devices) comprises a readily oxidizable metal, such as W.
The metal gate etch process is generally followed by a clean. The clean is used to strip the photoresist pattern, and remove the post etch residues while attempting to maintain selectivity to the exposed metal. A significant yet to be met challenge for this clean is to be able to strip the photoresist without significantly oxidizing the metal gate electrode layer, and without generating a residue that is impossible or at least difficult to remove.
This Summary is provided to comply with 37 C.F.R. §1.73, presenting a summary of the invention to briefly indicate the nature and substance of the invention. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims.
Embodiments of the present invention describe a new gate stack arrangement for CMOS integrated circuits (IC) that have the dual work function metal gate, and cleans that reduce residual particles and thus improve yield and reliability of such ICs. The new gate stack comprises one of the metal gate comprising materials (for PMOS devices) referred to herein as the first metal comprising layer being a readily oxidizable metal, such as W, while the other metal gate comprising material (for NMOS devices) comprises a silicide of the same first metal (e.g. WSi2). One embodiment of the invention comprises a multi-step wet cleaning sequence for cleaning a semiconductor wafer surface, that includes a first wet clean consisting essentially of sulfuric acid and a fluoride, a second wet clean after the first clean comprising a fluoride, and a third dilute wet clean after the second wet clean comprising a hydroxide and a peroxide. The third dilute wet clean comprises a volume ratio of the hydroxide to the peroxide is in a range from 1:2 to 2:1 and a volume ratio of the hydroxide combined with the peroxide to deionized (DI) water from 1:250 to 1:1,000. The third dilute wet clean is operable to remove particles without etching significant amounts of exposed metal.
The process integration for such dual work function metal gate arrangements can comprise selectively forming the silicide (e.g. over only the NMOS regions) from a first metal such as W by a conventional annealing process. The selective silicide process generally comprises a blanket deposition of a polysilicon or amorphous silicon layer on the first metal to form an intermediate gate stack. The intermediate gate stack is generally then patterned, such by plasma etching through the top polysilicon or amorphous silicon stopping on the metal (e.g. W). This etch process is followed by a series of cleans. A first clean is used to strip the masking pattern such as a photoresist pattern, and a multi-step wet clean sequence following the first clean is used to remove post etch residues while maintaining selectivity to the exposed metal (e.g. W). Significantly, cleans according to embodiments of the invention also have been found to minimize etch induced residue that is impossible or at least difficult to remove, such as arrangements of silicon and the gate electrode metal generated by the dry etch used to pattern the intermediate gate stack.
The present invention is described with reference to the attached figures, wherein like reference numerals are used throughout the figures to designate similar or equivalent elements. The figures are not drawn to scale and they are provided merely to illustrate the instant invention. Several aspects of the invention are described below with reference to example applications for illustration. It should be understood that numerous specific details, relationships, and methods are set forth to provide a full understanding of the invention. One having ordinary skill in the relevant art, however, will readily recognize that the invention can be practiced without one or more of the specific details or with other methods. In other instances, well-known structures or operations are not shown in detail to avoid obscuring the invention. The present invention is not limited by the illustrated ordering of acts or events, as some acts may occur in different orders and/or concurrently with other acts or events. Furthermore, not all illustrated acts or events are required to implement a methodology in accordance with the present invention.
Step 101 comprises providing a substrate having a semiconductor surface, wherein the semiconductor surface has PMOS regions (e.g. n-) for PMOS devices and NMOS regions (p-) for NMOS devices and an isolation structures (e.g. trench isolation) between the PMOS and NMOS devices. Step 102 comprises forming a gate dielectric layer on both PMOS (e.g. n-) and NMOS (e.g. p-) regions. The gate dielectric can be thermally grown (e.g. silicon oxide) or be a deposited gate dielectric, such as a high-k dielectric. The high-k dielectric generally has a k-value>10. Exemplary high-k dielectrics can include hafnium oxide, hafnium silicon oxide, hafnium silicon oxynitride, lanthanum oxide, zirconium oxide, zirconium silicon oxide, tantalum oxide, titanium oxide, barium strontium titanium oxide, barium titanium oxide, strontium titanium oxide, yttrium oxide, aluminum oxide, lead scandium tantalum oxide, and lead zinc niobate. The high-k dielectric can comprise both Hf and Zr. In one particular embodiment the high-k gate dielectric is an Hf comprising gate dielectric layer that comprises 1 nm to 5 nm of HfSiON, wherein the HfSiON comprises 30 to 60 at. % SiO2 and 2 to 20 at. % N with the balance being HfO. HfSiON can be formed by nitridizing HfSiO.
Step 103 comprises forming a first metal comprising layer on the gate dielectric layer, wherein the first metal comprising layer is capable of forming a silicide and is generally a readily oxidizable metal. In one embodiment of the invention the first metal comprising layer can comprise a refractory metal. As known in the art, the refractory metals include niobium (also known as columbium), tantalum, molybdenum, tungsten, and rhenium. Step 104 comprises forming a polysilicon or amorphous silicon layer on the first metal comprising layer to form an intermediate gate stack. Step 105 comprises forming a masking pattern on the intermediate gate stack. The masking pattern generally comprises photoresist, but may also comprise a hard mask material. Step 106 comprises etching using the masking pattern to form a patterned intermediate gate stack. The etching can comprise a plasma etch which etches through the top polysilicon or amorphous silicon layer for one of the device types (e.g. the PMOS devices) stopping on the first metal comprising layer.
The deposited post etch residue 205 is shown on both the first metal comprising layer 202 over the PMOS device region 220 and the photoresist layer over the NMOS device region 230. The deposited post edge residue 205 can generally comprise various residue materials including photoresist residue, silicon residue as well as silicon/metal comprising assemblies, with the metal being supplied by the etching of the first metal comprising layer during etching of the polysilicon or amorphous silicon layer 203. The assemblies can also comprise oxygen, or other species present during the etching of the polysilicon or amorphous silicon layer 203. The Present Inventors have found that some of the deposited post etch residue 205, such as the assemblies described above, if allowed to reach a significant annealing temperature, such as at least 450° C., tend to bond to the first metal comprising layer 202 forming one or more new residue materials that tend to not be possible to remove or are at least very difficult to remove. However, clean processes according to embodiments of the invention including the exemplary clean processes described below relative to steps 107 and 108 can be used to strip the photoresist pattern, and remove a large percentage of the deposited post etch residues 205 while maintaining selectivity to the exposed first metal comprising layer 202, without significantly oxidizing the first metal comprising layer 202 or generating a residue that is impossible or at least difficult to later remove.
Returning to
Step 108 generally comprises a multi-step wet cleaning sequence. One or more of the steps of the multi-step cleaning sequence can be performed in a spray tool, or be performed in conventional wet etch tanks. Step 108a comprises a first wet clean comprising sulfuric acid and a fluoride. The fluoride can comprise hydrogen fluoride (HF), ammonium fluoride, tetramethylammonium fluoride, ammonium hydrogen fluoride, fluorboric acid or tetramethylammonium tetrafluoroborate. The first wet clean is generally performed at a temperature of at least 40° C., such as between 60° C. and 120° C. In one particular embodiment the fluoride in the first wet clean comprises HF and the first wet clean further comprises deionized (DI) water, wherein a volume ratio (volumes described herein are all expressed as concentrated solutions, unless noted otherwise) of sulfuric acid, DI water and HF is A:B:1 wherein A is generally between 200 and 800, and B is generally between 2 and 50.
Step 108b comprises a second wet clean after the first clean comprising a fluoride. The fluoride can be one of the fluorides listed above. In one particular embodiment the fluoride in the second clean can comprises HF, wherein the second wet clean comprises concentrated HF diluted from 50:1 to 150:1 with DI water, generally performed at a temperature of 20 to 30° C. The multi-step solution cleaning sequence in step 108 can optionally also comprise a first DI water rinse between the first and the second wet clean and a second DI water rinse after the second wet clean, wherein the first and said second DI water clean comprises megasonic agitation for at least a portion of their respective times.
Step 108c can comprise a third wet clean after the second wet clean. The third wet clean can comprise a dilute solution of a hydroxide and a peroxide, such as the cleaning solution known in the art as a SC1 clean, which comprises a 1:1 aqueous mixture of ammonium hydroxide (NH4OH), hydrogen peroxide, and DI water. As known in the art, a peroxide is a compound that comprises an oxygen-oxygen single bond. As used herein, “peroxides” include peroxide forming materials. The simplest stable peroxide is hydrogen peroxide. Other peroxides include superoxides, and dioxygenyls.
More generally, the hydroxide can comprise a non-alkali metal comprising hydroxide, such as ammonium hydroxide or an organic non-alkali metal comprising hydroxide such as TMAH. The hydroxide can also comprise an alkali hydroxide comprising a group IA (except H) or group IIA metal. However, alkali hydroxide etching unlike non-alkali hydroxide etching, generally adds a subsequent step to remove the alkali metal. The peroxide can comprises hydrogen peroxide, and a concentration of the ammonium hydroxide:hydrogen peroxide: DI water can be from 1:1:500 to 1:1:2,000, such as 1:1:1,500. The third wet clean can be performed at a temperature from 25 to 40° C.
Step 109 comprises selectively forming the silicide (e.g. over only the NMOS regions 230) from the first metal comprising layer 202, such as by a conventional annealing process. Step 110 can comprise forming a barrier metal layer. Step 111 comprises forming a gate electrode filler layer, such as polysilicon or amorphous silicon. Step 112 can comprise forming an anti-reflective layer, such as an inorganic anti-reflective layer (IARC), on top of the gate electrode filler layer. Step 113 comprises lithography followed by an etch process to define the respective gate stacks over the PMOS and the NMOS regions. Step 114 comprises completing fabrication of the IC generally including LDD formation, spacer formation, source drain formation, as well as multi-layer metal processing and other back end of the line (BEOL) processing.
The following non-limiting Examples serve to illustrate selected embodiments of the invention. It will be appreciated that variations in proportions and alternatives in elements of the components shown will be apparent to those skilled in the art and are within the scope of embodiments of the present invention.
Wafers having the structure shown in
In a first inventive embodiment, a hydrogen nitrogen reducing ash with a pressure 10 mtorr; power=1,500 Watts, 200 Watt back bias and 50 sccm N2 and 150 sccm H2 at 20° C. was used to remove the photoresist layer 204. Reducing the back bias to 100 Watts was found to improve removal performance. The wet clean sequence used in the first embodiment comprised a first wet clean comprising a sulfuric acid/DI water/HF mixture at 80° C. for 45 seconds. The volume ratio of sulfuric acid, DI water and HF was A:B:1 wherein A was 400, and B was 25. The second wet clean which followed the first wet clean comprised 100:1 HF at 25° C. for 15 seconds. The third wet clean which followed the second wet clean comprised an ultra dilute SC1 clean (1:1:1,500) at 35° C. for 15 seconds followed by DI water agitated by megasonic energy rinse. The entire wafer surface was scanned. The surface analyzed was found to have 6,900 particles, with the residue particles and blisters generally being very small, generally in the size range from 0.25 to 0.35 μm.
Other related ash and wet clean sequence combinations were prepared for comparison to the first inventive embodiment described above. A first related combination comprised a hydrogen/nitrogen reducing ash followed by the first and second wet clean described above (no third wet clean). The surface analyzed was found to have 10,900 particles despite only scanning 70% of the wafer area (normalized to 15,517 particles). Large residue was found generally around 5 μm in size, and particle counts were so high that the particles may have masked blisters present.
A second related combination comprised an oxidizing ash followed by a reducing ash, followed by the first and second wet cleans described above (again, no third wet clean). The entire wafer surface was scanned. The surface analyzed was found to have 7,000 particles. Large residue was found generally around 5 μm in size, and the large residue may have again masked blisters present.
A third related combination comprised a reducing ash followed by an oxidizing ash followed by a reducing ash, followed by the first and second wet cleans described above (again, no third wet clean). The surface analyzed was found to have 11,600 particles despite only scanning 70% of the wafer area (normalized to 16,571 particles). Large residue was found generally around 5 μm in size, and particle counts were so high that the particles again could have masked blisters present.
While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example only, and not limitation. Numerous changes to the disclosed embodiments can be made in accordance with the disclosure herein without departing from the spirit or scope of the invention. Thus, the breadth and scope of the present invention should not be limited by any of the above described embodiments. Rather, the scope of the invention should be defined in accordance with the following claims and their equivalents.
Although the invention has been illustrated and described with respect to one or more implementations, equivalent alterations and modifications will occur to others skilled in the art upon the reading and understanding of this specification and the annexed drawings. In addition, while a particular feature of the invention may have been disclosed with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular application.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Furthermore, to the extent that the terms “including”, “includes”, “having”, “has”, “with”, or variants thereof are used in either the detailed description and/or the claims, such terms are intended to be inclusive in a manner similar to the term “comprising.”
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The Abstract of the Disclosure is provided to comply with 37 C.F.R. §1.72(b), requiring an abstract that will allow the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the following claims.
