Patent Publication Number: US-2020283898-A1

Title: High selectivity atomic layer deposition process

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims benefit of U.S. Provisional Application Ser. No. 62/813,911, filed Mar. 5, 2020 (Attorney Docket No. APPM/44016526/USL), of which is incorporated by reference in its entirety. 
    
    
     BACKGROUND 
     Field 
     Embodiments generally relate to methods for selectively forming a metal containing material on certain locations of a semiconductor substrate. More specifically, embodiments relate to methods for selectively forming a metal containing material on certain locations of a semiconductor substrate by an atomic layer deposition process for semiconductor manufacturing applications. 
     Description of the Related Art 
     Reliably producing sub-half micron and smaller features is one of the key technology challenges for next generation very large scale integration (VLSI) and ultra large-scale integration (ULSI) of semiconductor devices. However, as the limits of circuit technology are pushed, the shrinking dimensions of VLSI and ULSI technology have placed additional demands on processing capabilities. Reliable formation of gate structures on the substrate is important to VLSI and ULSI success and to the continued effort to increase circuit density and quality of individual substrates and die. 
     As the geometry limits of the structures used to form semiconductor devices are pushed against technology limits, the need for accurate formation with desired materials for the manufacture of structures having small critical dimensions and high aspect ratios and structures with certain desired materials has become increasingly difficult to satisfy. The conventional selective deposition process often cannot efficiently be confined and formed at the designated small dimensions on the substrate, resulting in undesired materials formed on the undesired locations of the substrate. Thus, the materials would be globally formed on the entire surface of such substrate without selectivity or be grown on the undesired locations of the substrate, thus making the selective deposition process difficult to achieve or even result in cross contamination on the substrate surface. 
     Thus, there is a need for improved methods for a deposition process suitable for advanced generation of semiconductor applications. 
     SUMMARY 
     Methods for depositing a metal containing material formed on a certain material of a substrate using an atomic layer deposition process for semiconductor applications are provided. In one embodiment, a method of forming a metal containing material on a substrate comprises pulsing a first gas precursor comprising a metal containing precursor to a surface of a substrate, pulsing a second gas precursor comprising a silicon containing precursor to the surface of the substrate, forming a metal containing material selectively on a first material of the substrate, and thermal annealing the metal containing material formed on the substrate. 
     In another embodiment, a method of forming a metal containing material on a substrate includes performing an atomic layer deposition process by alternatively pulsing a first and a second gas precursor to a surface of a substrate comprising a first and a second material, wherein the first gas precursor comprises a metal containing gas, selectively forming a metal containing material on the first material of the substrate, and thermally annealing the metal containing material 
     In yet another embodiment, a method of forming a metal containing material on a substrate includes selectively forming a metal containing layer on a silicon material on a substrate than on an insulating material on the substrate by an atomic layer deposition process, and maintaining a substrate temperature less than 150 degrees Celsius while performing the atomic layer deposition process. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments. 
         FIG. 1  depicts an apparatus that may be utilized to perform an atomic layer deposition (ALD) process; 
         FIG. 2  depicts an apparatus may be utilized to perform an thermal annealing processing process in accordance with one embodiment of the present disclosure; 
         FIG. 3  depicts a schematic view of a cluster processing system that includes the apparatus of  FIGS. 1 and 2 ; 
         FIG. 4  depicts a flow diagram of an example of a method for selectively forming a metal containing material on certain locations on a substrate; 
         FIGS. 5A-5G  depict one embodiment of a sequence for forming a metal containing material selectively on certain locations on the substrate during the manufacturing process according to the process depicted in  FIG. 4 ; 
         FIG. 6  depict another embodiment of a metal containing material selectively on certain locations on the substrate during the manufacturing process according to the process depicted in  FIG. 4 ; and 
         FIG. 7  depicts a thickness variation over time of a metal containing material disposed on different locations of the substrate with different materials. 
     
    
    
     To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation. 
     It is to be noted, however, that the appended drawings illustrate only exemplary embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments. 
     DETAILED DESCRIPTION 
     Methods for selectively depositing a metal containing material at a certain location on a structure formed on the substrate are provided. The structure may include a back-end structure, front-end structure, interconnection structure, passivation structure, fin structure, a gate structure, a contact structure, or any suitable structure in semiconductor devices. In one example, an atomic layer deposition process may be utilized to form a metal containing material on a certain surface, e.g., selectively form a certain type of a material on a substrate comprising two or more different surfaces made from different materials. In one example, a molybdenum containing material is formed by an atomic layer deposition (ALD) process. The ALD process utilizes at least two different precursors during the atomic layer deposition to form the molybdenum containing material selectively formed on a silicon surface at a temperature less than 150 degrees Celsius. 
       FIG. 1  is a schematic cross-sectional view of one embodiment of an atomic layer deposition (ALD) processing chamber  100 . The ALD processing chamber  100  includes a gas delivery apparatus  130  adapted for cyclic deposition, such as ALD or chemical vapor deposition (CVD). The terms ALD and CVD as used herein refer to the sequential introduction of reactants to deposit a thin layer over a substrate structure. The sequential introduction of reactants may be repeated to deposit a plurality of thin layers to form a conformal layer to a desired thickness. The chamber  100  may also be adapted for other deposition techniques along with lithography process. 
     The chamber  100  comprises a chamber body  129  having sidewalls  131  and a bottom  132 . A slit valve tunnel  133  formed through the chamber body  129  provides access for a robot (not shown) to deliver and retrieve a substrate  101 , such as a 200 mm, 300 mm or 450 mm semiconductor substrate or a glass substrate, from the chamber  100 . 
     A substrate support  192  is disposed in the chamber  100  and supports the substrate  101  during processing. The substrate support  192  is mounted to a lift  114  to raise and lower the substrate support  192  and the substrate  338  disposed thereon. A lift plate  116  is connected to a lift plate actuator  118  that controls the elevation of the lift plate  116 . The lift plate  116  may be raised and lowered to raise and lower pins  120  movably disposed through the substrate support  192 . The pins  120  are utilized to raise and lower the substrate  101  over the surface of the substrate support  192 . The substrate support  192  may include a vacuum chuck, an electrostatic chuck, or a clamp ring for securing the substrate  101  to the surface of the substrate support  192  during processing. 
     The substrate support  192  may be heated to heat the substrate  101  disposed thereon. For example, the substrate support  192  may be heated using an embedded heating element, such as a resistive heater, or may be heated using radiant heat, such as heating lamps disposed above the substrate support  192 . A purge ring  122  may be disposed on the substrate support  192  to define a purge channel  124  which provides a purge gas to a peripheral portion of the substrate  101  to prevent deposition thereon. 
     A gas delivery apparatus  130  is disposed at an upper portion of the chamber body  129  to provide a gas, such as a process gas and/or a purge gas, to the chamber  100 . A pumping system  178  is in communication with a pumping channel  179  to evacuate any desired gases from the chamber  100  and to help maintain a desired pressure or a desired pressure range inside a pumping zone  166  of the chamber  100 . 
     In one embodiment, the gas delivery apparatus  130  comprises a chamber lid  132 . The chamber lid  132  includes an expanding channel  137  extending from a central portion of the chamber lid  132  and a bottom surface  160  extending from the expanding channel  137  to a peripheral portion of the chamber lid  132 . The bottom surface  160  is sized and shaped to substantially cover the substrate  101  disposed on the substrate support  192 . The chamber lid  132  may have a choke  162  at a peripheral portion of the chamber lid  132  adjacent the periphery of the substrate  101 . The cap portion  172  includes a portion of the expanding channel  137  and gas inlets  136 A,  136 B. The expanding channel  137  has gas inlets  136 A,  136 B to provide gas flows from two similar valves  142 A,  142 B. The gas flows from the valves  142 A,  142 B may be provided together and/or separately. 
     In one configuration, valve  142 A and valve  142 B are coupled to separate reactant gas sources, but are coupled to the same purge gas source. For example, valve  142 A is coupled to a reactant gas source  138  and valve  142 B is coupled to reactant gas source  139 , which both valves  142 A,  142 B are coupled to purge a gas source  140 . Each valve  142 A,  142 B includes a delivery line  143 A,  143 B having a valve seat assembly  144 A,  144 B and includes a purge line  145 A,  145 B having a valve seat assembly  146 A,  146 B. The delivery line  143 A,  143 B is in communication with the reactant gas source  138 ,  139  and is in communication with the gas inlet  137 A,  137 B of the expanding channel  190 . The valve seat assembly  144 A,  144 B of the delivery line  143 A,  143 B controls the flow of the reactant gas from the reactant gas source  138 ,  139  to the expanding channel  190 . The purge line  145 A,  145 B is in communication with the purge gas source  140  and intersects the delivery line  143 A,  143 B downstream of the valve seat assembly  144 A,  144 B of the delivery line  143 A,  143 B. The valve seat assembly  146 A,  146 B of the purge line  145 A,  145 B controls the flow of the purge gas from the purge gas source  140  to the delivery line  143 A,  143 B. If a carrier gas is used to deliver reactant gases from the reactant gas source  638 ,  639 , the same gas may be used as a carrier gas and a purge gas (i.e., an argon gas may be used as both a carrier gas and a purge gas). 
     Each valve  142 A,  142 B may be a zero dead volume valve to enable flushing of a reactant gas from the delivery line  143 A,  143 B when the valve seat assembly  144 A,  144 B of the valve is closed. For example, the purge line  145 A,  145 B may be positioned adjacent the valve seat assembly  144 A,  144 B of the delivery line  143 A,  143 B. When the valve seat assembly  144 A,  144 B is closed, the purge line  145 A,  145 B may provide a purge gas to flush the delivery line  143 A,  143 B. In the embodiment shown, the purge line  145 A,  145 B is positioned as slightly spaced from the valve seat assembly  144 A,  144 B of the delivery line  143 A,  143 B so that a purge gas is not directly delivered into the valve seat assembly  144 A,  144 B when open. A zero dead volume valve as used herein is defined as a valve which has negligible dead volume (i.e., not necessary zero dead volume.) Each valve  142 A,  142 B may be adapted to provide a combined gas flow and/or separate gas flow of the reactant gas from the sources  138 ,  139  and the purge gas from the source  140 . The pulses of the purge gas may be provided by opening and closing a diaphragm of the valve seat assembly  146 A of the purge line  145 A. The pulses of the reactant gas from the reactant gas source  138  may be provided by opening and closing the valve seat assembly  144 A of the delivery line  143 A. 
     A control unit  180  may be coupled to the chamber  100  to control processing conditions. The control unit  180  comprises a central processing unit (CPU)  182 , support circuitry  184 , and memory  186  containing associated control software  183 . The control unit  180  may be one of any form of general purpose computer processors that can be used in an industrial setting for controlling various chambers and sub-processors. The CPU  182  may use any suitable memory  186 , such as random access memory, read only memory, floppy disk drive, compact disc drive, hard disk, or any other form of digital storage, local or remote. Various support circuits may be coupled to the CPU  182  for supporting the chamber  100 . The control unit  180  may be coupled to another controller that is located adjacent individual chamber components, such as the programmable logic controllers  148 A,  148 B of the valves  142 A,  142 B. Bi-directional communications between the control unit  180  and various other components of the chamber  100  are handled through numerous signal cables collectively referred to as signal buses  188 , some of which are illustrated in  FIG. 1 . In addition to the control of process gases and purge gases from gas sources  138 ,  139 ,  140  and from the programmable logic controllers  148 A,  148 B of the valves  142 A,  142 B, the control unit  180  may be configured to be responsible for automated control of other activities used in substrate processing, such as substrate transport, temperature control, chamber evacuation, among other activities, some of which are described elsewhere herein. 
       FIG. 2  is a schematic sectional view of a processing chamber  200  according to one embodiment of the disclosure. The processing chamber  200  may be used to process one or more substrates, including deposition of a material on an upper surface of a substrate, such as an upper surface  216  of a substrate  101  depicted in  FIG. 2 . The processing chamber  200  includes a chamber body  201  connected to, an upper dome  228  and a lower dome  214 . In one embodiment, the upper dome  228  may be fabricated from a material such as a stainless steel, aluminum, or ceramics including quartz, including bubble quartz (e.g., quartz with fluid inclusions), alumina, yttria, or sapphire. The upper dome  228  may also be formed from coated metals or ceramics. The lower dome  214  may be formed from an optically transparent or translucent material such as quartz. The lower dome  214  is coupled to, or is an integral part of, the chamber body  201 . The chamber body  201  may include a base plate  260  that supports the upper dome  228 . 
     An array of radiant heating lamps  202  is disposed below the lower dome  214  for heating, among other components, a backside  204  of a substrate support  207  disposed within the processing chamber  200 . During deposition, the substrate  101  may be brought into the processing chamber  200  and positioned onto the substrate support  207  through a loading port  203 . The lamps  202  are adapted to the heat the substrate  101  to a predetermined temperature to facilitate thermal decomposition of process gases supplied into the processing chamber to deposit a material on onto the upper surface  216  of the substrate  101 . The lamps  202  may be adapted to heat the substrate  101  to a temperature of about 300 degrees Celsius to about 1200 degrees Celsius, such as about 300 degrees Celsius to about 950 degrees Celsius. 
     The lamps  202  may include bulbs  241  surrounded by an optional reflector  243  disposed adjacent to and beneath the lower dome  214  to heat the substrate  101  as the process gas passes thereover to facilitate the deposition of the material onto the upper surface  216  of the substrate  101 . The lamps  202  are arranged in annular groups of increasing radius around a shaft  232  of the substrate support  207 . The shaft  232  is formed from quartz and contains a hollow portion or cavity therein, which reduces lateral displacement of radiant energy near the center of the substrate  208 , thus facilitating uniform irradiation of the substrate  101 . 
     In one embodiment, each lamp  202  is coupled to a power distribution board (not shown) through which power is supplied to each lamp  202 . The lamps  202  are positioned within a lamphead  245  which may be cooled during or after processing by, for example, a cooling fluid introduced into channels  449  located between the lamps  202 . The lamphead  245  conductively cools the lower dome  214  due in part to the close proximity of the lamphead  245  to the lower dome  214 . The lamphead  245  may also cool the lamp walls and walls of the reflectors  243 . If desired, the lampheads  245  may be in contact with the lower dome  214 . 
     The substrate support  207  may be moved vertically by an actuator (not shown) to a loading position below the processing position to allow lift pins  205  to contact the lower dome  214 . The lift pins  205  pass through holes  211  in the substrate support  207  and raise the substrate  101  from the substrate support  207 . A robot (not shown) may then enter the processing chamber  200  to engage and remove the substrate  408  therefrom through the loading port  203 . A new substrate is placed on the substrate support  207 , which then may be raised to the processing position to place the substrate  101 , with upper surface  216  wherein devices mostly formed thereon facing up, in contact with a front side  210  of the substrate support  207 . 
     The substrate support  207  disposed in the processing chamber  200  divides the internal volume of the processing chamber  200  into a process gas region  256  (above the front side  210  of the substrate support  207 ) and a purge gas region  258  (below the substrate support  207 ). The substrate support  207  is rotated during processing by a central shaft  232  to minimize the effects of thermal and process gas flow spatial non-uniformities within the processing chamber  200 , and thus facilitate uniform processing of the substrate  101 . The substrate support  207  is supported by the central shaft  232 , which moves the substrate  101  in an up and down direction  234  during loading and unloading, and in some instances, during processing of the substrate  101 . The substrate support  207  may be formed from a material having low thermal mass or low heat capacity, so that energy absorbed and emitted by the substrate support  207  is minimized. 
     In one embodiment, the upper dome  228  and the lower dome  214  are formed from an optically transparent or translucent material such as quartz. The upper dome  228  and the lower dome  214  are thin to minimize thermal memory. In one embodiment, the upper dome  228  and the lower dome  214  may have a thickness between about 3 mm and about 10 mm, for example about 4 mm. The upper dome  228  may be thermally controlled by introducing a thermal control fluid, such as a cooling gas, through an inlet portal  226  into a thermal control space  236 , and withdrawing the thermal control fluid through an exit portal  230 . In some embodiments, a cooling fluid circulating through the thermal control space  236  may reduce deposition on an inner surface of the upper dome  228 . 
     A liner assembly  262  may be disposed within the chamber body  201  and is surrounded by the inner circumference of the base plate  260 . In one embodiment, the liner assembly  262  may be fabricated from an optical transparent or translucent material, such as glass, quartz, including bubble quartz (e.g., quartz with fluid inclusions), sapphire, opaque quartz, and the like. Alternatively, the liner assembly  262  may be fabricated by a metallic material, such as aluminum containing materials if the material is protected from corrosion. 
     An optical pyrometer  218  may be disposed at a region above the upper dome  228 . The optical pyrometer  218  measures a temperature of the upper surface  216  of the substrate  101 . In certain embodiments, multiple pyrometers may be used and may be disposed at various locations above the upper dome  228 . A reflector  222  may be optionally placed outside the upper dome  228  to reflect infrared light that is radiating from the substrate  101  or transmitted by the substrate  101  back onto the substrate  101 . Due to the reflected infrared light, the efficiency of the heating will be improved by containing heat that could otherwise escape the processing chamber  200 . The reflector  222  can be made of a metal such as aluminum or stainless steel. The reflector  222  can have the inlet portal  226  and exit portal  230  to carry a flow of a fluid such as water for cooling the reflector  222 . If desired, the reflection efficiency can be improved by coating a reflector area with a highly reflective coating, such as a gold coating. 
     A plurality of thermal radiation sensors  240 , which may be pyrometers or light pipes, such as sapphire light pipes, may be disposed in the lamphead  245  for measuring thermal emissions of the substrate  101 . The sensors  240  are typically disposed at different locations in the lamphead  245  to facilitate viewing (i.e., sensing) different locations of the substrate  101  during processing. In embodiments using light pipes, the sensors  240  may be disposed on a portion of the chamber body  201  below the lamphead  245 . At least two sensors  240  are used, but more than two may be used. 
     Each sensor  240  views a zone of the substrate  101  and senses the thermal state of that zone. The zone may be oriented radially in some embodiments. For example, in embodiments where the substrate  101  is rotated, the sensors  240  may view, or define, a central zone in a central portion of the substrate  101  having a center substantially the same as the center of the substrate  101 , with one or more zones surrounding the central zone and concentric therewith. It is not required that the zones be concentric and radially oriented. In some embodiments, zones may be arranged at different locations of the substrate  101  in non-radial fashion. 
     Process gas supplied from a process gas supply source  273  is introduced into the process gas region  256  through a process gas inlet port  275  formed in the sidewall of the base plate  260 . Removal of the process gas through the gas outlet port  278  may be facilitated by a vacuum pump  280  coupled thereto. Purge gas supplied from a purge gas source  263  is introduced to the purge gas region  258  through a purge gas inlet port  264  formed in the sidewall of the base plate  260 . The purge gas inlet port  264  is disposed at an elevation below the process gas inlet port  275 . The purge gas inlet port  264  is configured to direct the purge gas in a generally radially inward direction. If desired, the purge gas inlet port  264  may be configured to direct the purge gas in an upward direction. During the film formation process, the substrate support  207  is located at a position such that the purge gas flows along flow path  261  across a back side  204  of the substrate support  207 . Without being bound by any particular theory, the flowing of the purge gas is believed to prevent or substantially avoid the flow of the process gas from entering into the purge gas region  258 , or to reduce diffusion of the process gas entering the purge gas region  258  (i.e., the region under the substrate support  207 ). The purge gas exits the purge gas region  258  (along flow path  266 ) and is exhausted out of the process chamber through the gas outlet port  278  located on the opposite side of the processing chamber  200  relative to the purge gas inlet port  264 . 
     During processing, a controller  282  receives data from the sensors  240  and separately adjusts the power delivered to each lamp  202 , or individual groups of lamps or lamp zones, based on the data. The controller  282  may include a power supply  284  that independently powers the various lamps  202  or lamp zones. The controller  282  can be configured to produce a desired temperature profile on the substrate  101 , and based on comparing the data received from the sensors  240 , the controller  282  may adjust the power to lamps and/or lamp zones to conform the observed (i.e., sensed) thermal data indicating of the lateral temperature profile of the substrate with to the desired temperature profile. The controller  282  may also adjust power to the lamps and/or lamp zones to conform the thermal treatment of one substrate to the thermal treatment of another substrate, to prevent chamber performance drift over time. 
       FIG. 3  depicts a plan view of a semiconductor processing system  300  that the methods described herein may be practiced. One processing system that may be adapted to benefit from the disclosure is a 300 mm or 450 mm Producer® processing system, commercially available from Applied Materials, Inc., of Santa Clara, Calif. The processing system  300  generally includes a front platform  302  where substrate cassettes  318  included in FOUPs  314  are supported and substrates are loaded into and unloaded from a loadlock chamber  309 , a transfer chamber  311  housing a substrate handler  313  and a series of tandem processing chambers  306  mounted on the transfer chamber  311 . 
     Each of the tandem processing chambers  306  includes two process regions for processing the substrates. The two process regions share a common supply of gases, common pressure control, and common process gas exhaust/pumping system. Modular design of the system enables rapid conversion from one configuration to any other. The arrangement and combination of chambers may be altered for purposes of performing specific process steps. Any of the tandem processing chambers  306  can include a lid according to aspects of the disclosure as described below that includes one or more chamber configurations described above with referenced to the processing chamber  100 ,  200  depicted in  FIG. 1  and/or  FIG. 2 . It is noted that the processing system  300  may be configured to perform a deposition process, etching process, curing processes, or heating/annealing process as needed. In one embodiment, the processing chambers  100 ,  200 , shown as a single chamber designed in  FIGS. 1 and 2 , may be incorporated into the semiconductor processing system  300 . 
     In one implementation, the processing system  300  can be adapted with one or more of the tandem processing chambers having supporting chamber hardware known to accommodate various other known processes such as atomic layer deposition process, chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, curing, or heating/annealing and the like. For example, the system  300  can be configured with one of the processing chambers  200  in  FIG. 2  as a thermal annealing process for annealing or one of the processing chambers  100  depicted in  FIG. 1  as an atomic layer deposition processing chamber for selectively forming a desired material layer on a certain location of the substrate. Such a configuration can maximize research and development fabrication utilization and, if desired, eliminate exposure of films as etched to atmosphere. 
     A controller  340 , including a central processing unit (CPU)  344 , a memory  342 , and support circuits  346 , is coupled to the various components of the semiconductor processing system  300  to facilitate control of the processes of the present disclosure. The memory  342  can be any computer-readable medium, such as random access memory (RAM), read only memory (ROM), floppy disk, hard disk, or any other form of digital storage, local or remote to the semiconductor processing system  300  or CPU  344 . The support circuits  446  are coupled to the CPU  344  for supporting the CPU in a conventional manner. These circuits include cache, power supplies, clock circuits, input/output circuitry and subsystems, and the like. A software routine or a series of program instructions stored in the memory  342 , when executed by the CPU  344 , executes the tandem processing chambers  306 . 
       FIG. 4  is a flow diagram of one embodiment of a process  400  of forming a metal containing material by an atomic layer deposition (ALD) process. Such atomic layer deposition of the process  400  may be performed in the processing chamber  100  depicted in  FIG. 1 . The structure may be any suitable structures formed on a semiconductor substrate, such as interconnection structure with conductive and non-conductive areas, a fin structure, a gate structure, a contact structure, a front-end structure, a back-end structure or any other suitable structures utilized in semiconductor applications.  FIGS. 5A-5G  and  FIG. 6  are schematic cross-sectional views of a portion of a composite substrate corresponding to various stages of the process  400 . The process  400  may be utilized to an interconnection structure both conductive and non-conductive areas formed on a substrate so as to form a metal containing material formed on certain locations of the structure with certain materials formed on the substrate. 
     The process  400  begins at operation  402  by providing a substrate, such as the substrate  502 , as shown in  FIG. 5A . In one embodiment, the substrate  502  may have a structure  550  formed on the substrate  502 . In one example, the structure  550  may be utilized for forming semiconductor devices. In the example depicted in  FIG. 5A , the structure  550  may include at least two different materials, such as a first material  504  and a second material  506 . In one example, the first material  504  may be a silicon material or a metal material and the second material  506  may be an insulating material, such as SiO 2 , SiON, SiN, SiOC, SiCOH, and the like. In the example wherein the first material  504  is a silicon material, the silicon material of the first material  504  may be the material from the substrate  502 . Thus, the substrate  502  may be patterned to form openings that allow the second material  506  to be filled therein. The second material  506  is an insulating material comprising oxide or other suitable materials, such as SiO 2 , SiON, SiOC, SiCOH or SiN. 
     In one example, the substrate  502  may include materials selected from a group consisting of crystalline silicon (e.g., Si&lt;100&gt; or Si&lt;111&gt;), silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon wafers and patterned or non-patterned wafers silicon on insulator (SOI), carbon doped silicon oxides, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire. The substrate  502  may have various dimensions, such as 200 mm, 300 mm, 450 mm or other diameter, as well as, being a rectangular or square panel. Unless otherwise noted, embodiments and examples described herein are conducted on substrates with a 200 mm diameter, a 300 mm diameter, or a 450 mm diameter substrate. In the embodiment wherein a SOI structure is utilized for the substrate  502 , the substrate  502  may include a buried dielectric layer disposed on a silicon crystalline substrate. In the embodiment depicted herein, the substrate  502  may be a crystalline silicon substrate. Moreover, the substrate  502  is not limited to any particular size or shape. The substrate  502  may be a round substrate having a 200 mm diameter, a 300 mm diameter or other diameters, such as 450 mm, among others. The substrate  502  may also be any polygonal, square, rectangular, curved or otherwise non-circular workpiece, such as a polygonal glass substrate used in the fabrication of flat panel displays. 
     Although the example depicted in  FIG. 5A  shown that the structure  550  is formed on the substrate  502 , it is noted that there may be further structures formed between the interconnection structure  550  and the substrate  502  as needed. In one example, a front-end structure, such as a gate structure and/or a contact structure may be formed between the structure  550  and the substrate  502  to enable functions of the semiconductor devices. 
     In one example, the insulating material for the second material  506  included in the structure  550  may be a dielectric material, such as silicon oxide material, doped silicon materials, low-k material, such as carbon containing materials. Suitable carbon containing materials include amorphous carbon, SiC, SiOC, doped carbon materials or any suitable materials. Suitable examples of the low-k insulating dielectric material includes SiO containing materials, SiN containing materials, SiOC containing materials, SiC containing materials, carbon based materials, or other suitable materials. 
     The insulating material may be formed by a plasma enhanced chemical vapor deposition (CVD), a flowable chemical vapor deposition (CVD), a high density plasma (HDP) chemical vapor deposition (CVD) process, atomic layer deposition (ALD), cyclical layer deposition (CLD), physical vapor deposition (PVD), or the like as needed. 
     At operation  404 , a first pulse of a first gas precursor is supplied onto the substrate surface in a processing chamber, such as the processing chamber  100  depicted in  FIG. 1 , to form a first monolayer  508   a  selectively on the first material  504  of the substrate  502 , as shown in  FIG. 5A . The first monolayer  508   a  may be a part of the metal containing material eventually desired to be formed on the substrate  502 . The first monolayer  508   a  is selected to predominantly form the first material  504  (e.g., a silicon material or a metal material) with compatible film qualities and characteristics to the first monolayer  508   a , but not to the second material  506  (e.g., an insulating material), so that the first monolayer  508   a  may be selectively formed on the surface  509  of the first material  504  of the substrate  502 , rather than globally formed across the substrate  502 , including the surfaces  510  of the second material  506 . 
     The atomic layer deposition (ALD) process as performed for process  400  is a chemical vapor deposition (CVD) process with self-terminating/limiting growth. The ALD process yields a thickness of only a few angstroms or in a monolayer level. The ALD process is controlled by distribution of a chemical reaction into two separate half reactions which are repeated in cycles. The thickness of the metal containing material formed by the ALD process depends on the number of the reaction cycles. 
     The first reaction of the operation  404  provides the first monolayer  508   a  being absorbed on the first material  504  on the substrate  502  and a second reaction (e.g., which will be performed at operation  406 ) provide a second monolayer being absorbed on the first monolayer  508   a . As the ALD process is very sensitive to the substrate conditions, the first monolayer  508   a  that forms on the first material  504  where the silicon material (or metal material) is located may not be able to adhere or form on the oxide material, such as the insulating material from the second material  506 , formed on the substrate  502 . Thus, by utilizing the differences of the material properties at different locations from the substrate, a selective ALD deposition process may be enabled that allows the precursors from the ALD deposition process to nucleate and grow on the nucleate sites provided from the silicon elements (or metal elements) from the first material  504 , while inert to the surfaces  510  from oxide material from the second material  506 . 
     In one example, the first gas precursor is a metal containing precursor, which is utilized to provide metal elements to form a metal containing material on the substrate  502 . Thus, the first monolayer  508   a  as formed on the first material  504  is a metal material. The metal elements sourced from the first gas precursor is selected to be easily absorbed and attached to the silicon elements (or metal elements) from the first material  504  from the substrate  502 . Thus, the selective ALD deposition process selectively grow the first monolayer  508   a  comprising metal elements on designated sites only, i.e., the silicon materials or metal materials form the first material  504 , without forming on the non-silicon or non-metal material (e.g., oxide material or insulating material) from the second material  506 . 
     During the ALD deposition process, a pulse of a first gas precursor (e.g., a first reactant) is supplied into the processing chamber, such as the processing chamber  100  depicted in  FIG. 1 , to form the first monolayer  508   a . It is believed that the first monolayer  508   a  is absorbed onto the first material  504  by a chemical reaction that allows the metal atoms from the first monolayer  508   a  to be securely adhered on the silicon or metal atoms from the first material  504 . Since the metal elements from the first monolayer  508   a  may have chemical properties different from the oxide material from the second material  506 , the molecules from the second material  506  may not be able to successfully adhere the metal atoms from the first monolayer  508   a , thus selectively allowing the metal atoms from the first monolayer  508   a  to be adhered on the silicon or metal atoms of the first material  504 . In this way, the subsequently formed second monolayer (e.g.,  512   a  shown in  FIG. 5C ) may selectively deposit on the first monolayer  508   a , thus enabling a continuing selective deposition of an ALD process. 
     In one example, the first gas precursor (e.g., a first reactant) utilized in the first pulse of reaction to form the first monolayer  508   a  includes metal containing gas precursor, such as a molybdenum (Mo) containing gas precursor. Suitable examples of the molybdenum (Mo) containing gas precursor include molybdenum hexafluoride (MoF 6 ), Mo(NMe 2 ) 4 , MoCl 5 , MoCl 6 , Mo(CO) 6 , (C 6 H 6 )Mo(CO) 3 , (C 6 H 3 Me 3 )Mo(CO) 3 , (Ph[ t Bu]N) 3 Mo and Mo(allyl) 4  and the like. 
     Strong adherence of atoms in each layers and absorbability of the layers of atoms onto the surface of substrate provide compact and secured bonding structures so as to render a film property with a high film density and high selectivity (compared to a chemical vapor deposition process). 
     The first pulse of reaction sourced from the first gas precursor at operation  402  lasts for a predetermined time interval. The term pulse as used herein refers to a dose of material injected into the process chamber. During pulsing of the first gas precursor, several process parameters are also regulated. In one embodiment, the process pressure is controlled at between about 0.01 Torr and about 20 Torr. 
     The processing temperature is maintained less than 150 degrees Celsius, such as between about 40 degrees Celsius and about 130 degrees Celsius, such as about 120 degrees Celsius. It is believed that the relatively low deposition temperature, such as less than 150 degrees Celsius, may assist gradually and slowly adhering the elements onto the selected type of the material on the substrate to achieve deposition selectivity. Furthermore, the relatively low deposition temperature prevents thermal decomposition which will lead to non-selective deposition across the global surface of the substrate. The relatively low deposition temperature also prevents desorption of surface species from the second material  506  that could leave reactive dangling bonds. 
     Thus, the first monolayer  508   a  shown in  FIG. 5B  may include Mo elements, after the first pulse of the first gas precursor. Each pulse of the first reaction may deposit the first monolayer  508   a  having a thickness between about 1 Å and about 5 Å. 
     At operation  406 , after pulsing of the first gas precursor, a purge gas may be supplied to the substrate surface. Between each pulse of the first precursor or/and a second precursor (which will be later performed at operation  408 ) and/or a reactive gaseous species, a purge gas or a purge gas mixture, such as a nitrogen gas, an inert gas (e.g., He or Ar) or the like, may be pulsed into the processing chamber in between each or multiple pulses of the first precursor or/and a second precursor and/or a reactive gaseous species to remove the by-products, impurities or residual precursor gas mixture which is unreacted/non-absorbed by the substrate surface (e.g., unreacted impurities from the reactant gas mixture or others) so they can be pumped out of the processing chamber. 
     The process parameters controlled during the operation  406  for pulsing the purge gas and/or purge gas mixture may be controlled similar to or the same as the pulsing of the first gas mixture at operation  404 . 
     At operation  408 , after the first reaction and a pump/purge process, a second gas precursor (e.g., a second reactant or called a co-reactant) is supplied to initiate a second reaction, forming a second monolayer  512   a  on the first monolayer  508   a , as shown in  FIG. 5C . The second precursor may be supplied with or without additional reactive gaseous species as needed. The second precursor is a silicon containing precursor. Suitable examples of the silicon containing precursor include SiH 4 , Si 2 H 6 , SiCl 4 , SiF 4 , TEOS and the like. In one example, the silicon containing gas is SiH 4  or Si 2 H 6 . The pulse of the second gas precursor initiate a second reaction which may deposit the second monolayer  512   a  having a thickness between about 1 Å and about 3 Å. 
     It is believed that the silicon elements provided from the second precursor may react with the metal elements from the first monolayer  508   a , forming a metal and silicon containing material selectively on the first material  504 . The silicon element tends to have a relatively higher reactivity to the first monolayer  508   a  than from the surface  510  of the second material  506 , as the metal elements from the first monolayer  508   a  contain reactive bonds or ligands that can be displaced. Thus, the silicon elements supplied from the second gas precursor reacts with the metal elements from the first monolayer  508   a , rather than adhered onto the surface  510  of the second material  506 , thus rendering and enabling the continuation of the selective deposition process. 
     The second reaction lasts for a predetermined time interval to form the second monolayer  512   a . During pulsing of the second precursor comprising silicon containing precursor, a reactive gaseous species may be supplied simultaneously with, alternatively, or sequentially with the second precursor (e.g., the Si containing precursor as one example) as need prior to, during or after the pulsing of the second gas precursor. 
     During supplying of the second precursor with or without the reactive gaseous species (e.g., the reactive gaseous species supplied after the first precursor), several process parameters are also regulated. In one embodiment, the process pressure is controlled at between about 0.01 Torr and about 10 Torr. 
     The processing temperature is maintained less than 150 degrees Celsius, such as between about 40 degrees Celsius and about 130 degrees Celsius, such as about 120 degrees Celsius. It is believed that the relatively low deposition temperature, such as less than 150 degrees Celsius, may assist gradually and slowly adhering the elements onto the selected type of the material on the substrate to achieve deposition selectivity. Furthermore, the relatively low deposition temperature prevents thermal decomposition which will lead to non-selective deposition across the global surface of the substrate. The relatively low deposition temperature also prevents desorption of surface species from the second material  506  that could leave reactive dangling bonds. 
     Thus, the first monolayer  508   a  and the second monolayer  512   a  as shown in  FIG. 5C  may include Mo elements as well as silicon elements, after the second pulse of the second precursor. 
     At operation  410 , after pulsing of the second gas precursor, a purge gas may be supplied to the substrate surface. Between each pulse of the first precursor or/and a second precursor (which will be later performed at operation  408 ) and/or a reactive gaseous species, a purge gas or a purge gas mixture, such as a nitrogen gas, an inert gas (e.g., He or Ar) or the like, may be pulsed into the processing chamber in between each or multiple pulses of the first precursor or/and a second precursor and/or a reactive gaseous species to remove the by-products, impurities or residual precursor gas mixture which is unreacted/non-absorbed by the substrate surface (e.g., unreacted impurities from the reactant gas mixture or others) so they can be pumped out of the processing chamber. 
     The process parameters controlled during the operation  410  for pulsing the purge gas and/or purge gas mixture may be controlled similar to or the same as the pulsing of the first gas precursor or the second gas precursor at operation  404  and  408  respectively. 
     It is noted that the first reaction at operation  404  and the second reaction at operation  408  (and the purge processes at operation  406  and  410 ) may be repeatedly performed, as indicated by the loop  412 , forming an additional first monolayer  508   b , as shown in  FIG. 5D  and yet another additional second monolayer  512   b , as shown in  FIG. 5E , until a desired thickness of the overall metal containing layer  520  is reached, as shown in  FIG. 5F . It is noted that the element/atom scale shown in  FIGS. 5B-5E  may be exaggerated for ease of explanation. 
     Alternatively, in an optional example, after operation  410 , the process  400  may further proceed to operation  414  by supplying a third gas precursor to the substrate surface. The third gas precursor (e.g., a third reactant or called a co-reactant) is supplied to initiate a third reaction, forming a third monolayer  514   a  on the second monolayer  512   a , as shown in  FIG. 6 . The third gas precursor may be supplied with or without additional reactive gaseous species as needed. The third precursor is an oxygen containing precursor. In one example, suitable examples of the oxygen containing precursor include H 2 O, O 2 , O 3 , CO 2 , H 2 O 2 , NO 2 , N 2 O, and the like. The oxygen containing gas is O 2  or O 3 . The pulse of the third gas precursor initiates the third reaction which may deposit the third monolayer  514   a  having a thickness between about 1 Å and about 3 Å. 
     Similarly, it is believed that the oxygen elements provided from the third gas precursor may react with the metal elements from the first monolayer  508   a  and the silicon elements from the second monolayer  512   a , forming a metal and silicon containing oxide material selectively on the first material  504 . The oxygen element tends to have a relatively higher reactivity to the first and the second monolayers  508   a ,  512   a  than from the surface  510  of the second material  506 , as the metal and silicon elements from the first and second monolayer  508   a ,  512   a  are at an excited and activated state. Thus, the oxygen elements supplied from the third gas precursor reacts with the metal and silicon elements from the first and second monolayer  508   a ,  512   a , rather than adhered onto the surface  510  of the second material  506 , thus rendering a selective deposition process. 
     The third reaction initiated from the third gas precursor at operation  414  may be similarly performed as the first and the second reactions at operation  404  and  408 . 
     Similarly, followed by operation  414 , an optional pump/purge process at operation  416  may also be performed to remove the surface residuals, excess reactive species and the like. The pump/purge process at operation  416  is similarly controlled or the same as the pump/purge process controlled at operations  406 ,  410 . 
     It is noted that the first reaction at operation  404 , the second reaction at operation  408  and the third reaction at operation  414  (and the purge processes at operation  406 ,  410  and  416 ) may be repeatedly performed, as indicated by the loop  420 , forming an additional first monolayer  508   b , additional second monolayer  512   b , and additional third monolayer until a desired thickness of the overall metal containing layer  520  is reached, as shown in  FIG. 5F . It is noted that the element/atom scale shown in  FIG. 6  may be exaggerated for ease of explanation. 
     In the embodiment wherein the operations  414 ,  416  are not performed, the operation  422  may be performed subsequent to the operation  410 . 
     At operation  422 , as discussed above, when a desired thickness (e.g., a predetermined number of cycles among operations  404  to  410 , or a predetermined number of cycles among operations  404  to  416 ) is reached, the metal containing layer  520  is selectively formed on the first material  504 , as shown in  FIG. 5F . The metal containing layer  520  has a thickness range from 10 Å and about 100 Å. As discussed above, based on the number of the cycles among the selected operations, composition of the resultant metal containing layer  520  may be different. For example, the metal containing layer  520  may be a MoSi layer when the process  400  is predominately performed by the loop  412  among operations  404  to  410 . Alternatively, the metal containing layer  520  may be a MoSiO layer when the process  400  is predominately performed by the loop  420  among operations  404  and  416 . Furthermore, based on different film property requirements, the operations as selected to perform may be altered or adjusted to render the metal containing layer  520  with different ratios of the elements among molybdenum, silicon and/or oxygen. For example, if additional elements are desired, an additional gas precursor, such as a fourth gas precursor and so on, may be used to introduce additional elements to the metal containing layer  520  as needed. 
     At operation  424 , optionally, an annealing process may be performed to thermally treat the metal containing layer  520 , forming a treated metal containing layer  522  selectively on the first material  504 , as shown in  FIG. 5G . During the annealing process, additional reacting gas may be supplied to incorporate further elements into the metal containing layer  520 . For example, during an annealing process, oxygen elements may be introduced and doped into the metal containing layer  520  as needed. In the example wherein the process  400  is performed utilizing the loop  412  between operation  404  to operation  410 , a third element, if desired, may be introduced, incorporated, or doped into the metal containing layer  520  by the annealing process at operation  424  to form the treated metal containing layer  522 . 
     The annealing process at operation  424  is performed to incorporate additional dopants or elements into the metal containing layer  520  as well as repair, densify and enhance the bonding structures of the metal containing layer  520 , forming the treated metal containing layer  522  with different components and lattice structures. For example, when two elements (e.g., Mo and silicon elements) are formed in the metal containing layer  520  (e.g., formed from the loop  412  of operations  404 - 410 ), the annealing process at operation  424  may assist incorporating the third element (e.g., oxygen elements) into the metal containing layer  520 , forming the treated metal containing layer  522  (e.g., a MoSiO layer). 
     Furthermore, the annealing process may also assist removing impurities from the metal containing layer  520 . 
     The thermal annealing process may be performed in a thermal annealing chamber, such as the processing chamber  200  depicted in  FIG. 2 . Alternatively, the thermal annealing process may be performed at the ALD processing chamber  100 , as depicted in  FIG. 1 , followed by the metal containing layer ALD deposition process without breaking vacuum. Alternatively, the annealing process may be performed in any processing chamber configured to provide enough thermal energy to metal containing layer  520 . The thermal annealing process may heat the substrate  502  to a temperature greater than 200 degrees Celsius, such as between about 250 degrees Celsius and about 400 degrees Celsius, for example between about 350 degrees Celsius. 
     During annealing, an annealing gas mixture (or an additional reacting gas) may be supplied. Gases that may be supplied in the annealing gas mixture may include an oxygen containing gas, such as O 2 , N 2 O, NO 2 , NO, O 3  and the like. In the example wherein additional elements are not necessarily required, a nitrogen containing gas, such as NH 3 , N 2 , and the like, an inert gas, such as Ar, He, Ne, Kr, Xe or the like, may be utilized to assist providing thermal energy to the metal containing layer  520 . 
     In some examples, the thermal annealing process performed at operation  424  may be a rapid thermal annealing process, laser annealing process, furnace annealing process or any suitable thermal annealing process as needed. 
     In one example, after the thermal annealing process at operation  424 , some impurities or byproduct, such as F elements from the first gas precursor, or carbon elements from the ambient embodiment, may be driven out, so as to increase the crystallinity structure or density of the resultant treated metal containing layer  522  by removing undesired elements from the film structure. 
       FIG. 7  depicts a thickness variation over numbers of the cycle pf precursor pulses performed to form the metal containing layer  520  on different locations with different materials from the substrate  502 . The thickness of the metal containing layer  520  grown on the first material  504  is shown by the trace line  704  while the thickness of the metal containing layer  520  grown on the second material  506  is shown by the trace line  702 . As indicated by the trace line  704 , with the increase of the numbers of the cycles from operation  404  to  410 , or from operation  404  to operation  416 , the metal containing layer  520  formed on the first material  504  is steadily grown and increased while with minimum growth on the second material  506 , as shown in the trace line  702 . Thus, the metal containing layer  520  is selectively and predominately formed on the first material  504 , such as a silicon material, rather than on the second material  506 , such as SiO 2 , SiN, SiON, SiOC, SiOCH and the like. 
     Thus, a selective deposition process is provided to a metal containing layer on different surfaces, e.g., different portions, of a substrate by a selective ALD process. Thus, a structure with desired different type of materials formed on different locations of the substrate may be obtained. 
     While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.