# Patent

## Title
Remote plasma radical treatment of silicon oxide

## Abstract

Embodiments described herein generally relate to methods for manufacturing flash memory devices. In one embodiment, the method includes generating a plasma comprising nitrogen-containing radicals in a remote plasma applicator, flowing the plasma comprising nitrogen-containing radicals into a processing region of the processing chamber where a semiconductor device is disposed, wherein the semiconductor device has a substrate comprising an oxide layer formed thereon, exposing an exposed surface of the oxide layer to the nitrogen-containing radicals, and incorporating nitrogen in the exposed surface of the oxide layer of the substrate.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of Ser. No. 13/658,594, filed Oct. 23, 2012, which claims benefit of U.S. provisional patent application Ser. No. 61/552,370, filed Oct. 27, 2011, which is herein incorporated by reference.


BACKGROUND
1. Field
Embodiments of the present disclosure generally relate to manufacturing semiconductor devices. More specifically, embodiments described herein relate to manufacture of floating gate NAND memory devices and other transistor gate dielectrics using an improved plasma applicator and process.
2. Description of the Related Art
Flash memory, such as NAND flash memory devices, is a commonly used type of non-volatile memory in widespread use for mass storage applications. The NAND flash memory devices typically have a stacked type gate structure in which a tunnel oxide (TO), a floating gate (FG), an inter-poly dielectric (IPD), and a control gate (CG) are sequentially stacked on a semiconductor substrate. The floating gate, the tunnel oxide, and the underlying portion of the substrate generally form a cell (or memory unit) of the NAND flash memory device. A shallow trench isolation (STI) region is disposed in the substrate between each cell adjacent to the tunnel oxide and the floating gate to separate the cell from adjacent cells. During writing of the NAND flash memory devices, a positive voltage is applied to the control gate which draws electrons from the substrate into the floating gate. For erasing data of the NAND flash memory devices, a positive voltage is applied to the substrate to discharge electrons from the floating gate and through the tunnel oxide. The flow of electrons is sensed by a sensing circuitry and results in the returns of “0” or “1” as current indicators. The amount of electrons in the floating gate and “0” or “1” characteristics form the basis for storing data in the NAND flash memory devices.
The floating gate is typically isolated from the semiconductor substrate by the tunnel oxide and from the control gate by the inter-poly dielectric, which prevents the leakage of electrons between, for example, the substrate and the floating gate or the floating gate and the control gate. To enable continued physical scaling of the NAND flash memory device, a nitridation process has been used by the industry to incorporate nitrogen into the surface of the floating gate to improve the reliability of the tunnel oxide or to suppress dopant diffusion out of the floating gate. The surface nitridation of the tunnel oxide is also desirable for minimizing the flat-band voltage (Vfb) shift and mobility degradation. Therefore, the percentage of the nitrogen at the floating gate and the tunnel oxide interface is critical to improve the NAND flash program window. For NAND Flash applications, it has been desirable to increase the interface N % concentration from nominally 3% to much higher levels of 6%-12%, which, however, requires high thermal budgets in excess of 1100° C. and 60 seconds. However, the manufacturers of NAND Flash memories typically prefer thermal budgets less than 1000° C. and 30 seconds to prevent the dopant in the floating gate from diffusing out. In addition, it has been observed that the nitridation process also undesirably incorporates nitrogen into shallow trench isolation regions. Nitrogen incorporated in the shallow trench isolation region between neighboring floating gate structures forms a charge leakage path which can negatively impact final device performance.
Therefore, there is a need for improved methods and an apparatus without having the above-mentioned issues.
SUMMARY
Embodiments described herein generally relate to methods for manufacturing flash or DRAM memory devices. In various embodiments, the method generally includes a radical nitridation process to incorporate nitrogen into exposed surfaces of a tunnel oxide or SiO2 gate dielectric formed on a substrate. In one embodiment, a method for processing a semiconductor device in a processing chamber is provided. The method generally includes generating a plasma comprising nitrogen-containing radicals in a remote plasma applicator, flowing the plasma comprising nitrogen-containing radicals into a processing region of the processing chamber where the semiconductor device is disposed, wherein the semiconductor device has a substrate having an oxide layer formed thereon, exposing an exposed surface of the oxide layer to the nitrogen-containing radicals, and incorporating nitrogen in the exposed surface of the oxide layer of the substrate.
In another embodiment, a method for processing a semiconductor device in a processing chamber is provided. The method generally includes exposing the semiconductor device to a nitrogen-containing gas, the semiconductor device having a substrate having an oxide layer formed thereon and a shallow trench isolation disposed adjacent to the oxide layer, flowing a gas mixture comprising nitrogen-containing gas and/or a non-reactive gas into a remote plasma applicator, exciting the gas mixture to produce a plasma comprising nitrogen-containing radicals and/or radicals from the non-reactive gas, flowing the plasma comprising substantially of nitrogen-containing radicals and/or radicals from the non-reactive gas into the processing region of the processing chamber where the semiconductor device is disposed in the presence of the nitrogen-containing gas to activate the nitrogen-containing gas, exposing an exposed surface of the oxide layer to the nitrogen-containing radicals from the activated nitrogen-containing gas, and incorporating nitrogen in the exposed surface of the oxide layer of the substrate.



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 present disclosure may admit to other equally effective embodiments.
FIG. 1 illustrates a schematic cross-sectional view of an exemplary semiconductor device that can be made with a method and an apparatus according to one embodiment of the disclosure.
FIG. 2 illustrates a schematic view of a remote plasma system in accordance with one embodiment of the disclosure.
FIG. 3 illustrates a schematic and fragmentary cross-sectional side view of an exemplary delivery pipe for use in supplying radicals of a plasma to an RTP apparatus according to one embodiment of the disclosure.
FIG. 4 illustrates a schematic and fragmentary top view of a delivery pipe of FIG. 3 and an RTP apparatus in accordance with an embodiment of the disclosure.
FIG. 5 illustrates a method of fabricating a NAND flash memory device according to one embodiment of the present disclosure.
FIGS. 6A-6D illustrate stages of fabrication of a NAND flash memory device in accordance with the embodiments of the present disclosure.
FIG. 7 illustrates a method of fabricating a NAND flash memory device according to another embodiment of the present disclosure.



DETAILED DESCRIPTION
The present disclosure describes an apparatus and method for incorporating radicals of a plasma into a substrate or a material on a semiconductor substrate using a remote plasma source. In general, plasma sources generated by, for example, an energetic excitation of gaseous molecules consisting of a plasma of charged ions, radicals, and electrons. The inventors of the present disclosure recognize that radicals of a plasma react in a much more desirable manner with silicon or polysilicon material on a substrate, than ions or a mixture of radicals and ions. In that regard, the present disclosure provides an apparatus and a method of eliminating the majority of the ions of the plasma such that only radicals of the plasma react with silicon or polysilicon material on a substrate, thereby obtaining a greater selectivity of processing of silicon or polysilicon material on the substrate.
The present disclosure is not intended to be limited to a particular device since the apparatus and methods described herein can be used for the manufacture of semiconductor devices and structures suitable for narrow pitch applications. As used herein, narrow pitch applications include half-pitches of 32 nm or less (e.g., device nodes of 32 nm or less). The term “pitch” as used herein refers to a measure between the parallel structures or the adjacent structures of the semiconductor device. The pitch may be measured from side to side of the same side of the adjacent or substantially parallel structures. The semiconductor devices and structures may be utilized in applications having greater pitches as well. The semiconductor devices may be, for example, NAND or NOR flash memory, or other suitable devices.
Exemplary NAND Flash Memory Device
FIG. 1 illustrates a schematic cross-sectional view of an exemplary semiconductor device, such as a NAND flash memory device 100, that can be made with the apparatus of the present disclosure. The memory device 100 generally includes a substrate 102 having a tunnel oxide layer 104 disposed thereon. A floating gate 106 is disposed on the tunnel oxide layer 104. The floating gate 106, the tunnel oxide layer 104, and the underlying portion of the substrate 102 form a cell 103 (or memory unit) of the memory device 100. Each cell 103 of the memory device 100 may be separated, for example, by a shallow trench isolation (STI) region 108 which is disposed in the substrate 102 between each cell 103 (e.g., adjacent to the tunnel oxide layer 104 and floating gate 106, where the STI region 108 separates the cell 103 from adjacent cells 105 and 107). The memory device 100 further includes a control gate layer 112 and an inter-poly dielectric (IPD) layer 110 disposed between the floating gate 106 and the control gate layer 112. The IPD layer 110 separates the floating gate 106 from the control gate layer 112.
The substrate 102 may include a suitable material such as crystalline silicon (e.g., Si<100> or Si<111>), silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon wafers, patterned or non-patterned wafers, silicon on insulator (SOI), carbon doped silicon oxides, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, or the like. In some embodiments, the substrate 102 comprises silicon.
The tunnel oxide layer 104 may include silicon and oxygen, such as silicon oxide (SiO2), silicon oxynitride (SiON), or high-k dielectric materials, such as aluminum-(Al), hafnium-(Hf), or lanthanum-(La), zirconium-(Zr) based oxides or oxynitrides, or silicon nitrides (SixNy), in single or layered structures (e.g., SiO2/high-k/SiO2), or the like. The tunnel oxide layer 104 may have any suitable thickness, for example, between about 5 nm to about 12 nm. The tunnel oxide layer 104 may have a width, within each cell, substantially equivalent to the width of a base of the floating gate 106. The STI region 108 may include silicon and oxygen, such as silicon oxide (SiO2), silicon oxynitride (SiON), or the like.
The floating gate 106 typically includes a conductive material, such as silicon, polysilicon, metals, or the like. The floating gate 106 has a configuration suitable to facilitate disposing portions of the control gate layer 112 between adjacent cells (e.g., between cells 103, 105, and 107). As such, the floating gate may be formed in an inverted “T” shape. As used herein, the term inverted “T” refers generally to the geometry of the structure wherein an upper portion of the floating gate 106 is relieved with respect to a base of the floating gate 106. Such relief provides room for the IPD layer 110 to be formed over the floating gate 106 without completely filling the gap between adjacent floating gates 106, thereby allowing a portion of the control gate layer 112 to be disposed between adjacent floating gates 106.
The IPD layer 110 may include any suitable single or multi-layer dielectric materials. An exemplary single layer IPD may include SiO2, SiON, or a high-k dielectric material as discussed above with respect to tunnel oxide layer 104, or the like. An exemplary multi-layer IPD may be a multi-layer “ONO” structure (not shown) including a first oxide layer, a nitride layer, and a second oxide layer. The first and second oxide layers typically include silicon and oxygen, such as silicon oxide (SiO2), silicon oxynitride (SiON), or the like. The nitride layer typically comprises silicon and nitrogen, such as silicon nitride (SiN), or the like. In some embodiments, a multi-layer IPD layer comprising SiO2/high-k/SiO2 (such as, SiO2/Al2O3/SiO2) can also be used as the IPD layer 110. The IPD layer 110 may be deposited to a thickness of between about 10 nm to about 15 nm.
The control gate layer 112 may be deposited atop the IPD layer 110 to form a control gate. The control gate layer 112 typically comprises a conductive material, such as polysilicon, metal, or the like. The inverted T shape of the floating gate 106 enables a larger surface area, located between adjacent floating gates (for example, those of cells 103 and 105), for the control gate late 112. The increased surface area of the control gate layer 112 may advantageously improve capacitive coupling between a sidewall of the floating gate 106 and the control gate, and may reduce parasitic capacitance between adjacent floating gates, floating gate interference, noise, or the like.
Optionally, prior to IPD deposition, a dielectric layer 113 may be conformally formed on the exposed surface of the floating gate 106. Specifically, the dielectric layer 113 is selectively formed mainly on the exposed surface of the floating gate 106, with little or no formation of the dielectric layer 113 on the STI region 108 or any other dielectric films under the identical plasma conditions (will be discussed in detail below). With the dielectric layer 113 selectively formed mainly on floating gate 106, the reliability of the tunnel oxide and/or suppression of dopant diffusion out of the floating gate 106 are improved while enabling scaling of the IPD film stack thickness.
The dielectric layer 113 may be a nitride layer such as silicon nitride or silicon oxynitride. The nitride layer may be formed by exposing the field surface 114 and sidewall 115 of the floating gate 106 to nitrogen containing radicals. Nitrogen containing radicals, such as N, NH, NO, NH2, or NH3, may be created with the aid of some excitation, for instance, a plasma excitation, a photo excitation, an electron-beam excitation, or intense heat. Nitridation process may be performed by thermal means alone, by plasma means alone, or by a combination of the two. In one embodiment, the surfaces of the floating gate 106 are exposed to nitrogen containing radicals using a selective plasma nitridation process. The nitrogen containing radicals will react preferentially with the surface of the floating gate 106 (formed of silicon or polysilicon, for example) during the selective plasma nitridation process, rather than the surface of the STI region 108 (formed of silicon oxide, for example) due to lower Si—Si bond-breaking energies (222 kJ/mol) compared to Si—O bond-breaking energies (452 kJ/mol). As radicals are not reactive enough to break Si—O bond, the selective plasma nitridation process forms nitrides of silicon faster than nitrides of silicon oxide, resulting in a significantly greater concentration of nitrogen-containing material, i.e., dielectric layer 113 formed of, for example, Si—N bonds, at the field surface 114 and sidewall 115 of the floating gate 106 as opposed to STI region 108 between the adjacent floating gates 106. Since the nitrogen-containing material or dielectric layer 113 is not present in significant amounts at STI region 108, the undesired charge leakage path between neighboring floating gate structures does not occur.
Radicals are preferred because ions have high chemical activity compared to radicals and compared to the bond energies listed above (1st ionization energy of N2=1402 kJ/mol; atomization energy of N2=473 kJ/mol), so ions do not achieve the selectivity of radicals. Selectivity, defined as concentration of nitrogen in silicon divided by concentration of nitrogen in oxide after a given deposition process, may be between about 10:1 and about 100:1, such as between about 20:1 and about 70:1, for example about 40:1. Greater exposure time may improve the selectivity.
High radical density versus ion density may be achieved by a high pressure plasma process using, for example, a pressure between about 0.3 Torr and 20 Torr, for example, about 5 Torr or above. The high pressure encourages ions to recombine with electrons quickly, leaving neutral radical species and inactive species. In some embodiments, a radical gas is formed. In some embodiments, remote plasma may be used to selectively generate radical species by various methods. The remote plasma generator, for example a microwave, RF, or thermal chamber, may be connected to a processing chamber through a delivery pipe. The delivery pipe, as will be described in more detail below with respect to FIGS. 3 and 4, may be a relatively long pathway positioned at an angle relative to the processing chamber to encourage recombination of ionic species along the pathway before reaching the processing region. The radicals flowing through the delivery pipe may flow into the chamber through a showerhead or radical distributor, or through a portal entry in a side wall of the chamber at a flow rate between about 1 slm and about 20 slm, such as between about 5 slm and about 20 slm, for example about 10 slm. Higher pressures and lower flows are believed to promote collisions. Nitrogen radicals may be formed in one embodiment by exposing a nitrogen containing gas, such as nitrogen, ammonia, or a mixture thereof, optionally with a carrier gas such as helium, to microwave power between about 1-3 kW at a pressure above about 5 Torr. The nitridation process may be performed at a substrate temperature between about 300° C. and about 1200° C., for example between about 800° C. and about 1000° C., which may be increased as the nitridation proceeds to combat surface saturation. Heating may be performed using lamp heating, laser heating, use of a heated substrate support, or by plasma heating.
In certain embodiments, various ion filters, such as electrostatic filters operated at a bias of, for example, about 200V (RF or DC), wire or mesh filters, or magnetic filters, any of which may have a dielectric coating, may be used between the remote plasma source and the processing chamber. In other embodiments, residence time in the remote plasma generator may be modulated using gas flow of reactive species such as nitrogen containing species or gas flow of non-reactive species such as argon or helium. In some embodiments, radical half-life may be extended by using an ion filter with low pressure plasma generation. Low pressure operation may be facilitated by integrating a processing chamber with a remote plasma chamber without using an O-ring to seal the pathway between the two chambers. Uniformity of radical flow into a processing chamber from remote plasma generation chamber may be improved using a shaped connector to provide intimate control of flow patterns.
The present disclosure as described herein contemplates that substantially all ions present in the plasma at the plasma generation (with the radicals) are eliminated prior to coming in contact with the surface of the floating gate 106 (formed of silicon or polysilicon, for example) during the selective plasma nitridation process, rather than the surface of the STI region 108 (formed of silicon oxide, for example). One way positively charged ions are eliminated is by combining with electrons (also present in the plasma at the plasma generation) to return to a non-ionic or charge neutral state. A plasma may be substantially free of the majority of the ions by separating the plasma generation source from the substrate location, e.g., the reaction site, by a distance longer than the lifetime of the ions at a given plasma discharge rate. In this manner, the radicals survive the travel distance to the substrate, but ions do not and instead lose their ionic character and become charge neutral.
Exemplary Remote Plasma System
FIG. 2 illustrates an exemplary remote plasma system 200 may benefit from embodiments of the present disclosure. Particularly, the remote plasma system 200 may be used to selectively form a nitride layer on a silicon or polysilicon surface of a semiconductor structure, such as a NAND flash memory device 100. The remote plasma system 200 may include a rapid thermal processing (RTP) apparatus 201, such as Centura® RTP commercially available from Applied Materials, Inc., located in Santa Clara, Calif. Other types of thermal reactors may be substituted for the RTP apparatus such as, for example, RPN, RPO, Vantage RadiancePlusTM RTP, Vantage RadOXTM RTP, Radiance® RTP, or other similar chambers/reactors available from Applied Materials Inc. of Santa Clara, Calif.
As can be seen in FIG. 2, coupled to the RTP apparatus 201 is a plasma applicator 280 used to remotely provide radicals of a plasma to the RTP apparatus 201. The RTP apparatus 201 generally includes a processing region 213 enclosed by a side wall 214 and a bottom wall 215. The upper portion of side wall 214 may be sealed to a window assembly 217 by “O” rings. A radiant energy light pipe assembly 218 (enclosed by an upper side wall 224) is positioned over and coupled to window assembly 217. Light pipe assembly 218 may include a plurality of tungsten halogen lamps 219 each mounted into light pipes 221 and positioned to adequately cover the entire surface area of wafer or substrate 101. Window assembly 217 may include a plurality of short light pipes 241. A vacuum can be produced in the plurality of light pipes 241 by pumping through a tube 253 connected to one of the light pipes 241 which is in turn connected to the rest of the pipes.
A wafer or substrate 101 containing the NAND flash memory device 100 is supported by a support ring 262 within a processing region 213. Support ring 262 is mounted on a rotatable cylinder 263. By rotating cylinder 263, the support ring 262 and the wafer or substrate 101 are caused to rotate during processing. Bottom wall 215 of RTP apparatus 201 may be coated or provided with a reflector 211 for reflecting energy onto the backside of wafer or substrate 101. The RTP apparatus 201 may include a plurality of fiber optic probes 271 positioned through the bottom wall 215 of RTP apparatus 201 to detect the temperature of the wafer or substrate.
The plasma applicator 280 generally includes a body 282 surrounding a tube 284 where a plasma of ions, radicals, and electrons is generated. The tube 284 may be made of quartz or sapphire. The tube 284 preferably does not form any electrical bias that might attract charged particles, e.g., ions. A gas inlet 286 is disposed at one end of the body 282 and opposes to a gas outlet 288 that is located at the other end of the body 282. The gas outlet 288 is in fluid communication with the RTP apparatus 201 through a delivery pipe 290 such that radicals of the plasma generated within the tube 284 are supplied to the processing region 213 of the RTP apparatus 201. The gas outlet 288 may have a diameter larger than gas inlet 286 to allow the excited radicals to be efficiently discharged at desired flow rate and to minimize the contact between the radicals and the tube 284. If desired, a separate orifice may be inserted into tube 284 at the gas outlet 288 to reduce the tube's inner diameter. The diameter of the gas outlet 288 (or orifice, if used) can be selected to optimize the pressure differential between the processing region 213 and the plasma applicator 280 for nitridation efficiency.
A gas source 292 of nitrogen-containing gas, including, but not limited to, N2 gas, may couple to a gas inlet 286 via a first input of a three-way valve 294 and a valve 297 used to control the flow rate of gas released from the gas source 292. A second input of the three-way valve 299 may be coupled to another process gas source 298 including, but not limited to, oxygen-containing gas, silicon-containing gas, or inner gas. A flow controller 296 is connected to the three-way valve 294 to switch the valve between its different positions, depending upon which process is to be carried out. The flow controller 296 also functions in a similar fashion to control the three-way valve 294 and the valve 317 to provide an appropriate process gas flow from gas source 298 to the process chamber.
The plasma applicator 280 may be coupled to an energy source (not shown) to provide an excitation energy, such as an energy having a microwave frequency, to the plasma applicator 280 to excite the process gas traveling from the gas source 292 into a plasma. In the case where nitrogen-containing gas, for example, N2, is used, the microwave excitation in plasma applicator 280 produces N* radicals, positively charged ions such as N+ and N2+, and electrons in the tube 284. By locating the plasma applicator 280 remotely from the processing region 213 of RTP apparatus 201, a plasma source can be selectively generated to limit the composition of the plasma exposed to substrate 101 to predominantly radicals. It has been observed that ions collisions can be further promoted by using an improved delivery pipe 290 such that all or the majority of ions generated by the excitation of the process gas to form a plasma outlive their ionic lifetime and become charge neutral before reaching the processing region 213. In other words, the composition of the plasma that is supplied to the inlet port 275 of the RTP apparatus 201 is predominantly radicals.
FIG. 3 illustrates a schematic and fragmentary cross-sectional side view of an exemplary delivery pipe 300 that may be used in place of the delivery pipe 290 of FIG. 2 according to one embodiment of the present disclosure. For the purpose of simplicity and clarity of illustration, elements in the drawings have not been drawn to scale. The delivery pipe 300 generally includes a mounting sleeve 302 and an inlet member 304 connecting to the mounting sleeve 302. The mounting sleeve 302 and the inlet member 304 each include a hollow cylindrical body defining a longitudinally extending space, for example, sleeve passageway 306 and inlet passageway 308. The profile of the passageway 306, 308 may be any shape such as circular, oval, square, rectangular, or irregular. One end of the mounting sleeve 302 may be bolted to the gas outlet 288 of the body 282 of the plasma applicator 280 (partially shown) so that the sleeve passageway 306 in the mounting sleeve 302 is aligned with and coupled to the tube 284 at the gas outlet 288. Another end of the mounting sleeve 302 is connected to the inlet member 304 so that the inlet passageway 308 in the inlet member 304 is substantially aligned with the sleeve passageway 306 in the mounting sleeve 302. In certain examples, the diameter of the mounting sleeve 302 may be gradually reduced along the longitudinal axis of the mounting sleeve 302 to match the diameter of the inlet member 304. The mounting sleeve 302 and the inlet member 304 may be made of a material that does not cause recombination of the N* radicals. For example, the mounting sleeve 302 and the inlet member 304 may be made of silicon, silicon nitride, boron nitride, carbon nitride, sapphire or alumina (Al2O3). While the delivery pipe 300 is shown and described as two separate components (i.e., the mounting sleeve 302 and the inlet member 304) being connected to one another, the present disclosure contemplates a delivery pipe formed from a single-piece integrated body with a passageway connecting to the inlet port 275 of the RTP apparatus 201.
As can be better seen in FIG. 4, which illustrates a schematic and fragmentary top view of the delivery pipe 300 and the RTP apparatus 201, the inlet member 304 may be configured as an adapter which is coupled to the inlet port 275 in the side wall 214 of the RTP apparatus 201. It should be noted that some elements in FIG. 4 have been omitted and not drawn to scale for the purpose of simplicity and clarity of illustration. The inlet member 304 may include a flange 310 extending wholly around the outer surface of the inlet member 304. A portion of the inlet member 304 may be extended into the side wall 214 such that an outermost face 312 of the flange 310 is bolted to the interior surface 214b of the side wall 214. Alternatively, the outermost face 312 of the flange 310 may be bolted to the exterior surface 214a of the side wall 214 and configured in a way that the inlet passageway 308 is coupled to the inlet port 275. In either case, the delivery pipe 300 is coupled to the inlet port 275 in such a way that a longitudinal axis “A” of the inlet passageway 308 in the inlet member 304 intersect at an angle θ with respect to a longitudinal axis “B” of the inlet port 275. The flange 310 may extend in a direction at a desired angle “α” relative to the longitudinal axis “A” of the inlet passageway 308 as long as that the outermost face 312 of the flange 310 is substantially flush with interior surface 214b of the side wall 214.
In one embodiment, the angle “α” may range from about 20 degrees to about 80 degrees, such as about 45 degrees to about 70 degrees. The angle θ between the longitudinal axis “A” of the inlet passageway 308 and the longitudinal axis “B” of the inlet port 275 may range between about 10 degrees and about 70 degrees, such as about 20 degrees and about 45 degrees. In one example, the angle α is about 45 degrees or above, for example about 60 degrees. The angle α or θ should not be limited as defined herein and may vary as necessary. Having the delivery pipe 300 positioned at an angle relative to the inlet port 275 promotes collision of ions or reaction of ions with electrons or other charged particles since the ions lose their momentum through collisions when hitting the interior surface of the inlet port 275. Therefore, substantially all ions created by the excitation by the energy source are eliminated prior to entering the processing region 213. While the delivery pipe 300 is shown and described to include the flange 310, the flange 310 may be omitted as long as the delivery pipe 300 is coupled to the RTP apparatus 201 at an angle that would promote collision of ions or reaction of ions with electrons or other charged particles.
In addition to the bent pipe structure as described herein, the delivery pipe 300 may be constructed of a length such that, for a given flow rate of a process gas (e.g., a given plasma generation rate), substantially all ions are extinguished or reacted with electrons or other charged particles to lose their excited state prior to existing the delivery pipe 300. The length of tube 284 and delivery pipe 300 necessary to extinguish substantially all the ions of a plasma at a given source gas flow rate may be determined experimentally or by lifetime calculations. In one embodiment, the tube 284 may have a length of about 5 inches to about 12 inches with an inside diameter of about 0.5 inches to about 2 inches. The length of the delivery pipe 300 (including passageways 306, 308) may vary from about 5 inches to about 25 inches, for example about 16 inches or above. The diameter of the passageway 306, 308 may be adjusted to optimize the pressure differential between the plasma applicator 280 and the processing region 213. In one embodiment, the diameter of the passageway 306, 308 is in a range between about 0.5 inches and about 2 inches, for example about 0.65 inches and about 1.5 inches in diameter. If desired, either one or both of the passageways 306, 308 may have a diameter gradually decreasing or increasing in the direction of flow to promote ion loss. In various embodiments, the total length of the tube 284 and the delivery pipe 300 may be between about 8 inches to about 35 inches, for example about 20 inches to about 35 inches. It is believed that a converging flow of plasma will promote ions collisions. The compression ratio, defined as cross sectional area of plasma generation area, (e.g., the tube 284) to cross sectional area of smallest diameter before the inlet port 275 (e.g., the inlet passageway 308) may be about 2 or above, for example between about 5 and about 10.
By separating the plasma generation area (i.e., plasma applicator 280) and the processing region 213 physically with an improved delivery pipe 300 being positioned at an angle relative to an inlet port 275 of the RTP apparatus that promotes recombination of ionic species, greater selectivity of nitridation of silicon or polysilicon floating gate 106 is obtained. In an embodiment where a NAND flash memory device having a floating gate 106 with silicon or polysilicon surface is treated with a selective nitridation process performed by the apparatus described herein, selectivity of nitridation of silicon or polysilicon floating gate 106 to STI region 108 may be increased to up to about 100:1 with a nitrogen dose of about 5×1015 atoms/cm2 to about 15×1015 atoms/cm2, such as about 20×1015 atoms/cm2 or up, for example about 25×1015 atoms/cm2, in the surface of silicon or polysilicon floating gate 106.
Exemplary Remote Plasma Radical Treatment of Gate Oxides
As discussed above, the manufacturers of NAND Flash memories need a lower thermal budget solution to incorporate nitrogen at the interface between the floating gate and the tunnel oxide. It has been observed by the inventors that the thermal budget for the nitrogen incorporation in the surface of the floating gate can be lowered by using radical activation of species. FIG. 5 depicts a method 500 of fabricating a NAND flash memory device according to one embodiment of the present disclosure. The method 500 is illustratively described with reference to FIGS. 6A-6C, which depicts stages of fabrication of a NAND flash memory device 600 in accordance with the embodiments of the method 500. The method 500 includes a radical nitridation process to incorporate nitrogen into exposed surfaces of the tunnel oxide followed by a floating gate formation process.
The method 500 generally begins at 502 by introducing nitrogen-containing gas into a remote plasma applicator which is driven with, for example, microwave, RF, or thermal energy. In one embodiment, the nitrogen-containing gas is introduced into the plasma applicator 280 as depicted in FIG. 2. The remote plasma generator may be connected to a processing chamber, for example, a rapid thermal processing (RTP) apparatus 201 as depicted in FIG. 2, through a delivery pipe. The delivery pipe may be positioned at an angle relative to an inlet port of the RTP apparatus, as discussed above with respect to FIGS. 3 and 4, so as to promote recombination of ionic species. The nitrogen-containing gas may be provided from a gas source, for example, the gas source 292 depicted in FIG. 2. In various embodiments, the nitrogen-containing gas may include, but is not limited to, nitrogen (N2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), hydrazine (N2H4), and mixtures thereof. In certain embodiments, the nitrogen-containing gas may include a gas mixture comprising NH3 and N2, a gas mixture comprising NH3 and H2, a gas mixture comprising NH3, N2, and H2, or a gas mixture comprising N2 and H2. In certain embodiments, hydrazine (N2H4) may be used in place of or in combination with NH3 in the gas mixture with N2 and H2. Alternatively, the nitrogen-containing gas may include lower substituted hydrazines (N2R2, wherein each R is independently hydrogen, a methyl, ethyl, propyl, vinyl, or propenyl group), and lower amines (NRaHb, wherein a and b are each integers from 0 to 3 and a+b=3, and each R is independently hydrogen, a methyl, ethyl, propyl, vinyl, or propenyl group), amides (RCONR′R′′, wherein R, R′, and R′′ are each independently hydrogen, a methyl, ethyl, propyl, vinyl, or propenyl group), imines (RR′C═NR′′, wherein R, R′, and R′′ are each independently hydrogen, a methyl, ethyl, propyl, vinyl, or propenyl group), or imides (RCONR′COR′′, wherein R, R′, and R′′ are each independently hydrogen, a methyl, ethyl, propyl, vinyl, or propenyl group). The nitrogen-containing gas may be optionally mixed with non-reactive gases, such as one or more of nitrogen gas (N2), helium (He), argon (Ar), neon (Ne), xenon (Xe), or the like.
At box 504, the nitrogen-containing gas in the plasma applicator 280 is excited to produce nitrogen-containing radicals such as N, NO, NH, or NH2. The nitrogen-containing gas may be exposed to a plasma in order to enhance the radical generation. The nitrogen-containing gas may be activated by exposure to an excitation energy such as microwave, UV, RF, intense heat, or electron synchrotron radiation. In one embodiment, the plasma applicator 280 is coupled to a microwave source having a microwave frequency to excite and dissociate the nitrogen-containing gas traveling from the gas source 292 into a plasma containing nitrogen-containing radicals. In one embodiment, the microwave source is a 2.45 GHz microwave source. The microwave source may be operated at a power level between about 1,000 W and 5,000 Watts, for example, 3,000 Watts.
High radical density versus ion density may be achieved by a high pressure plasma process using, for example, pressure between about 1 Torr and about 10 Torr. The high pressure is believed to encourage ions to recombine with electrons quickly, leaving neutral radical species and inactive species. In the case where ammonia gas (NH3) is used to produce nitrogen-containing radicals, the ammonia gas may be excited and dissociated in plasma applicator 280 to yield a plasma containing N* radicals, H* radicals, and/or NH* radicals. The excitation of ammonia gas may be performed at low microwave power between about 1 kW to about 3 kW. At low power, less dissociation of ammonia produces NHx* radicals without substantially dissociate the ammonia molecule. Therefore, more NHx* radicals can be delivered to the rapid thermal processing (RTP) apparatus 201, thereby limiting the composition of the plasma exposed to the device 100 to predominantly NHx* radicals.
At box 506, the plasma comprising substantially of nitrogen-containing radicals is flowed into the processing region 213 of the RTP apparatus 201 where semiconductor device is disposed. In one embodiment, the semiconductor device is a partially fabricated NAND flash memory device having a tunnel oxide. The plasma is substantially free of the majority of the ions by separating the plasma generation area (i.e., plasma applicator 280) from the processing region 213 by a distance longer than the lifetime of the ions at a given plasma discharge rate, and by using an improved delivery pipe 300 positioned at an angle relative to an inlet port 275 of the RTP apparatus that promotes recombination of ionic species, as discussed above with respect to FIGS. 2-4. The partially fabricated NAND flash memory device 600 is generally illustrated in FIG. 6A, which include a substrate 602 (similar to the substrate 102 depicted in FIG. 1) having a tunnel oxide layer 604 (similar to the tunnel oxide layer 104 depicted in FIG. 1) disposed thereon. A shallow trench isolation region 608 (similar to the STI region 108 depicted in FIG. 1) may be disposed adjacent to the tunnel oxide layer. The tunnel oxide layer 604 may include silicon and oxygen, such as silicon oxide (SiO2), silicon oxynitride (SiON), or high-k dielectric materials, as discussed above with respect to FIG. 1. The exposure of the surface 605 of the tunnel oxide layer 604 to nitrogen-containing radicals results in a high nitrogen incorporation in the exposed surface 605 of the tunnel oxide layer 604, forming a nitrogen region 603 as shown in FIG. 6B. In one embodiment, the nitrogen region 603 may have a thickness between about 0.1 nm and about 5 nm. The nitrogen region 603 may have a nitrogen concentration of about 4%, for example, about 8% or above. The nitrogen region 603 may act as a barrier layer and prevent dopant in the subsequently formed floating gate 606 from diffusing through the tunnel oxide layer 604.
The nitrogen-containing radicals may flow into the processing region 213 at a flow rate between about 1 slm and about 20 slm, such as between about 5 slm and about 20 slm, for example about 10 slm. During the process of nitrogen incorporation, the partially fabricated NAND flash memory device 600 may be positioned in a processing region of a process chamber, for example, the rapid thermal processing (RTP) apparatus 201, under a non-reactive atmosphere and subjected to a temperature between about 300° C. to about 1050° C. In cases where activated NH* radicals are delivered into the RTP apparatus 201, the temperature of the substrate 602 may be maintained between about 400° C. to about 1000° C. In cases where activated NO* radicals are delivered into the RTP apparatus 201, the temperature of the substrate 602 may be maintained between about 800° C. to about 1000° C. Gases which are considered non-reactive include, but are not limited to, nitrogen gas (N2), helium (He), argon (Ar), neon (Ne), and xenon (Xe). Pressure in the processing region of the RTP apparatus 201 may be controlled between about 0.1 Torr and 50 Torr, for example between about 2 Torr to about 20 Torr, such as between about 5 Torr to 10 Torr.
At box 508, a conductive material, such as silicon, polysilicon, metals, or the like, is deposited atop the tunnel oxide layer to form a floating gate 606 (similar to the floating gate 106 depicted in FIG. 1), as shown in FIG. 6C. While not discussed here, other fabrication steps used to complete the NAND flash memory device are contemplated. An exemplary NAND flash memory device is generally depicted in FIG. 1. The process described herein enables incorporation of nitrogen at the interface between the floating gate 606 and the tunnel oxide 604 by reacting activated nitrogen-containing radicals at exposed surface 605 of the tunnel oxide layer 604, thus improving the film electrical properties at lower thermal budgets less than 1000° C.
FIG. 7 depicts a method 700 of fabricating a NAND flash memory device according to another embodiment of the present disclosure. The method 700 is illustratively described with reference to FIGS. 6A-6D, which depicts stages of fabrication of a NAND flash memory device 600 in accordance with the embodiments of the method 700. The method 700 includes a radical nitridation process to incorporate nitrogen into exposed surfaces of the tunnel oxide followed by a floating gate formation process.
The method 700 generally begins at 702, where a partially fabricated NAND flash memory device having a tunnel oxide layer may be provided to a processing region of a processing chamber, for example, the rapid thermal processing (RTP) apparatus 201 as depicted in FIG. 2. The partially fabricated NAND flash memory device is illustrated in FIG. 6A as discussed above.
At box 704, a nitrogen-containing gas is flowed into the processing region 213 of the RTP apparatus 201 where the partially fabricated NAND flash memory device 600 is disposed. The partially fabricated NAND flash memory device 600 having the tunnel oxide layer 604 is exposed to the nitrogen-containing gas. The nitrogen-containing gas may be similar to the nitrogen-containing gas as discussed above in box 502. In one embodiment, the nitrogen-containing gas includes ammonia (NH3). In another embodiment, the nitrogen-containing gas includes nitric oxide (NO). The RTP apparatus 201 may be operated at a pressure between about 1 Torr and about 5 Torr.
At box 706, a gas mixture containing a nitrogen-containing gas is flowed into a remote plasma applicator, for example, the plasma applicator 280 as depicted in FIG. 2. The remote plasma generator may be connected to the RTP apparatus 201 through a delivery pipe to promote recombination of ionic species before entering the processing region, as discussed above with respect to FIGS. 3 and 4. In various embodiments, the nitrogen-containing gas may include, but is not limited to, nitrogen (N2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), hydrazine (N2H4), and mixtures thereof. Alternatively, the gas mixture may include non-reactive gases such as helium (He), argon (Ar), neon (Ne), xenon (Xe), or the like. In certain embodiments, the gas mixture may include both the nitrogen-containing gas and non-reactive gases.
At box 708, the gas mixture in the plasma applicator 280 is excited to produce nitrogen-containing radicals such as N, NO, NH, or NH2 and/or radicals from non-reactive gases such as He* or Ar* etc. The dissociated gas mixture may contain free radicals such as N* radicals, N2* radicals, Ar*, He* radicals, ions, atoms, and molecules thereof, and electrons, depending upon the gas mixture chosen. The gas mixture may be activated by exposure to an excitation energy such as microwave, UV, RF, intense heat, or electron synchrotron radiation. In one embodiment, the gas mixture is exposed to a 2.45 GHz microwave source operating at a power level between about 1,000 W and 5,000 Watts, for example, about 3,000 Watts, at a pressure about 1 Torr and about 10 Torr.
At box 710, the plasma comprising substantially of nitrogen-containing radicals and/or radicals from non-reactive gases is flowed into the processing region 213 of the RTP apparatus 201 where the partially fabricated NAND flash memory device 600 having the tunnel oxide 604 is disposed in the presence of the nitrogen-containing gas. The plasma comprising substantially of nitrogen-containing radicals and/or radicals from non-reactive gases may flow into the processing region at a flow rate between about 1 slm and about 20 slm, such as between about 5 slm and about 20 slm, for example about 10 slm. During the process of nitrogen incorporation, the partially fabricated NAND flash memory device 600 may be positioned in the processing region under a non-reactive atmosphere. Gases which are considered non-reactive include, but are not limited to, nitrogen gas (N2), helium (He), argon (Ar), neon (Ne), and xenon (Xe). Pressure in the processing region of the RTP apparatus 201 may be controlled between about 0.1 Torr and 50 Torr, for example between about 2 Torr to about 20 Torr, such as between about 5 Torr to 10 Torr.
The plasma containing substantially of N* radicals, N2* radicals, Ar* radicals, or He* radicals (may vary depending upon the gas mixture chosen) may react with the NH3 gas or NO gas that is previously filled within the processing region 213 through an alternate gas inject (not shown in FIG. 4) to produce N* radicals, H* radicals, NO radicals, and/or NH* radicals. In cases where the RTP apparatus 201 is previously filled with NO gas, the temperature of the substrate 602 may be maintained between about 800° C. to about 1000° C. during the nitridation process. In cases where the RTP apparatus 201 is previously filled with NH3 gas, the temperature of the substrate 602 may be maintained between about 400° C. to about 1000° C. during the nitridation process. The excitation of NH3 gas may be performed at low microwave power between about 1 kW to about 3 kW without substantially dissociate the ammonia molecule. Therefore, the partially fabricated NAND flash memory device 600 is exposed predominantly to NHx* radicals.
The exposure of the surface 605 of the tunnel oxide layer 604 to these nitrogen-containing radicals results in a high nitrogen incorporation in the exposed surface 605 of the tunnel oxide layer 604, forming a nitrogen region 603 as shown in FIG. 6B. In one embodiment, the nitrogen region 603 may have a thickness between about 0.1 nm and about 5 nm. The nitrogen region 603 may have a nitrogen concentration of about 4%, for example, about 8% or above. The nitrogen region 603 may act as a barrier layer and prevent dopant in the subsequently formed floating gate 606 from diffusing through the tunnel oxide layer 604.
In an alternative embodiment shown in FIG. 6D, prior to the deposition of the tunnel oxide layer 604, a surface 607 of the substrate 602 may be exposed to plasma activated species generated from a nitrogen-containing gas such as NO or N2O to incorporate nitrogen (denoted as 610) in the exposed surface 607. With the subsequent nitridation process as described with respect to FIGS. 5 and 7, the interface between the substrate 602 and the tunnel oxide layer 604 and the interface between the tunnel oxide layer 604 and the subsequently formed floating gate 606 may both provide a nitrogen region 603, 610 to further improve the NAND flash program window.
At box 712, a conductive material, such as silicon, polysilicon, metals, or the like, is deposited atop the tunnel oxide layer to form a floating gate 606 (similar to the floating gate 106 depicted in FIG. 1), as shown in FIG. 6C. While not discussed here, other fabrication steps used to complete the NAND flash memory device are contemplated. An exemplary NAND flash memory device is generally depicted in FIG. 1. The process described herein enables incorporation of nitrogen at the interface between the floating gate 606 and the tunnel oxide 604 by reacting activated nitrogen-containing radicals at exposed surface 605 of the tunnel oxide layer 604, thus improving the film electrical properties at lower thermal budgets less than 1000° C.
While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

## Claims

1. A method for processing a semiconductor device in a processing chamber, comprising:
generating a plasma comprising nitrogen-containing radicals in a remote plasma applicator;
eliminating majority of the ions from the plasma before introducing the plasma comprising nitrogen-containing radicals into a processing region of the processing chamber where the semiconductor device is disposed, wherein the semiconductor device comprises a substrate having an oxide layer formed thereon, wherein eliminating majority of the ions from the plasma comprises flowing the plasma into a delivery member disposed in fluid communication with the processing region through an inlet port, the inlet port is formed in a sidewall of the processing chamber and a longitudinal axis of the delivery member is at an angle is about 20 degrees to about 80 degrees with respect to a longitudinal axis of the inlet port;
exposing an exposed surface of the oxide layer to the nitrogen-containing radicals; and
incorporating nitrogen in the exposed surface of the oxide layer of the substrate.

2. The method of claim 1, wherein the oxide layer comprises silicon oxide (SiO2), silicon oxynitride (SiON), or high-k dielectric materials.

3. The method of claim 1, wherein the nitrogen-containing radicals comprise N radicals, NO radicals, NH radicals, or NH2 radicals.

4. The method of claim 3, wherein generating the plasma comprising nitrogen-containing radicals further comprises pressurizing a processing region of the remote plasma applicator to a pressure from about 1 Torr and about 10 Torr.

5. The method of claim 4, wherein the nitrogen-containing radicals comprise NH radicals and the remote plasma applicator is coupled to a microwave source operated at a power level between about 1 kW and 3 kW.

6. The method of claim 5, wherein exposing the exposed surface of the oxide layer to the nitrogen-containing radicals further comprises maintaining the substrate at a temperature between about 400° C. and about 1,000° C.

7. The method of claim 4, wherein the nitrogen-containing radicals comprises NO radicals.

8. The method of claim 7, wherein exposing the exposed surface of the oxide layer to the nitrogen-containing radicals further comprises maintaining the substrate at a temperature between about 800° C. and about 1,000° C.

9. The method of claim 1, wherein the delivery member is disposed between the remote plasma applicator and the processing chamber.

10. The method of claim 1, wherein substantially all ions are eliminated from the plasma before introducing the plasma comprising nitrogen-containing radicals into the processing region of the processing chamber.

11. The method of claim 10, wherein the semiconductor device has a layer formed thereon, and the layer comprises silicon oxide (SiO2), silicon oxynitride (SiON), or high-k dielectric materials and the substrate comprises crystalline silicon, silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon, silicon on insulator (SOI), carbon doped silicon oxides, silicon nitride, germanium, gallium arsenide, glass, or sapphire.

12. A method for processing a semiconductor device in a processing chamber, comprising:
exciting a gas mixture comprising nitrogen-containing gas and/or a non-reactive gas in a remote plasma applicator to produce a plasma comprising nitrogen-containing radicals and/or radicals from the non-reactive gas;
flowing the plasma comprising nitrogen-containing radicals and/or radicals from the non-reactive gas into a delivery member disposed in fluid communication with a substrate processing region of the processing chamber through an inlet port, the inlet port is formed in a sidewall of the processing chamber and a longitudinal axis of the delivery member is at an angle is about 20 degrees to about 80 degrees with respect to a longitudinal axis of the inlet port; and
exposing an exposed surface of a layer formed on the semiconductor device to the plasma to incorporate nitrogen in the exposed surface of the layer.

13. The method of claim 12, wherein the delivery member is disposed between the remote plasma applicator and the processing chamber.

14. The method of claim 12, wherein the layer comprises silicon oxide (SiO2), silicon oxynitride (SiON), or high-k dielectric materials and the substrate comprises crystalline silicon, silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon, silicon on insulator (SOI), carbon doped silicon oxides, silicon nitride, germanium, gallium arsenide, glass, or sapphire.

15. The method of claim 12, wherein nitrogen-containing gas comprises nitrogen (N2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), hydrazine (N2H4), or mixtures thereof.

16. The method of claim 12, wherein the non-reactive gas comprises nitrogen gas (N2), helium (He), argon (Ar), neon (Ne), or xenon (Xe).

17. The method of claim 12, wherein exciting the gas mixture to produce the plasma comprising nitrogen-containing radicals and/or radicals from the non-reactive gas comprises pressurizing a processing region of the remote plasma applicator to a pressure from about 1 Torr and about 10 Torr.

18. The method of claim 17, wherein the nitrogen-containing radicals comprise NH radicals and the remote plasma applicator is coupled to a microwave source operated at a power level between about 1 kW and 3 kW.

19. The method of claim 12, wherein exposing the exposed surface of the layer to the plasma further comprises maintaining the substrate at a temperature between about 400° C. and about 1,000° C.

20. A method for processing a semiconductor device in a processing chamber, comprising:
flowing a plasma comprising nitrogen-containing radicals from a remote plasma applicator into a processing region of the processing chamber where the semiconductor device is disposed, wherein the nitrogen-containing radicals are flowed into a delivery member disposed in fluid communication with the processing region through an inlet port, the inlet port is formed in a sidewall of the processing chamber and a longitudinal axis of the delivery member is at an angle is about 20 degrees to about 80 degrees with respect to a longitudinal axis of the inlet port; and
exposing a surface of the semiconductor device to the nitrogen-containing radicals.