# Patent

## Title
Low temperature formation of high quality silicon oxide films in semiconductor device manufacturing

## Abstract

Silicon oxide layer is deposited on a semiconductor substrate by PECVD at a temperature of less than about 200° C. and is treated with helium plasma to reduce stress of the deposited layer to an absolute value of less than about 80 MPa. Plasma treatment reduces hydrogen content in the silicon oxide layer, and leads to low stress films that can also have high density and low roughness. In some embodiments, the film is deposited on a semiconductor substrate that contains one or more temperature-sensitive layers, such as layers of organic material or spin-on dielectric that cannot withstand temperatures of greater than 250° C. In some embodiments the silicon oxide film is deposited to a thickness of between about 100-200 Å, and is used as a hardmask layer during etching of other layers on a semiconductor substrate.

## Background
FIELD OF THE INVENTION
The present invention pertains to methods of forming layers of material on a semiconductor substrate. Specifically, the invention pertains to methods for forming silicon oxide layers by plasma-enhanced chemical vapor deposition (PECVD).
BACKGROUND OF THE INVENTION
Fabrication of semiconductor devices typically involves deposition and patterning of several layers of different materials. When several layers are deposited in a stack, stress characteristics of deposited layers become particularly important because highly stressed materials can lead to disruption in alignment of layers in a stack, buckling, delamination, and, ultimately, to patterning inaccuracy, and semiconductor device failure.
Most film deposition is associated with the introduction of residual stress in the deposited film due to both extrinsic factors (e.g., thermal expansion coefficient mismatch) and/or intrinsic factors (e.g., defects and/or dislocations within lattice). The stress can be either compressive or tensile depending, for instance, on the characteristics of the substrate, the type of film being deposited, its properties, the manner of its deposition, etc. Compressive stress in the deposited films can lead to blistering or buckling of the film whereas tensile stress may lead to film cracking. Additionally, the wafer distortion induced by these stresses can cause reliability issue in other device layers and, generally, adversely impact electrical and optical performance, as well as the mechanical integrity of the fabricated semiconductor device. Thus, in semiconductor device fabrication, film stress is a major concern of the device layer integration strategy.
SUMMARY OF THE INVENTION
Silicon oxide is widely used in semiconductor device manufacturing as a dielectric layer material, and is often deposited by plasma-enhanced chemical vapor deposition processes (PECVD). There is currently a need to deposit silicon oxide by PECVD at low temperature because many integration schemes involve substrates having layers of temperature-sensitive materials (e.g., organic dielectrics) that cannot withstand high temperature PECVD. However, conventional low temperature PECVD provides silicon oxide films having unacceptably high stress values. In addition, silicon oxide PECVD films deposited at low temperature are found to have high hydrogen content and relatively low density, which makes them less attractive for use as hardmasks.
It was unexpectedly discovered that plasma treatment, and, particularly, helium plasma treatment of silicon oxide films obtained by low temperature PECVD, modifies the films and is capable of reducing film stress to less than about 80 MPa in absolute value. Further, the plasma treatment increases density of the formed films such that low stress films with densities of at least 2.05 g/cm3, and at least 2.1 g/cm3 can be obtained.
In one aspect, a method for processing a semiconductor substrate is provided, wherein the method includes: (a) providing a semiconductor substrate to a PECVD process chamber; (b) depositing a layer of silicon oxide on the semiconductor substrate by PECVD at a temperature of less than about 200° C. (e.g., at a temperature of less than about 180° C.), wherein the depositing comprises flowing a silicon-containing precursor, an oxygen-containing reactant, and, optionally, an inert gas, such as helium, into the PECVD process chamber and forming a plasma; (c) stopping flow of the silicon-containing precursor after deposition; and (d) treating the deposited layer of silicon oxide with a plasma at a temperature of less than about 200° C. to thereby modify the deposited layer and to reduce the stress of the deposited layer to an absolute value of less than about 80 MPa. Silicon oxide films having stress of less than about 50 MPa and even less than about 10 MPa in absolute value can be obtained. In one example the deposition of the silicon oxide layer is performed by forming a plasma in a mixture of SiH4 (silicon-containing precursor), CO2 (oxygen-containing reactant), and helium (an inert gas) at a pressure of between about 1.5-5 torr. In some embodiments the method involves increasing power used for plasma generation from a first power level used in the deposition of the silicon oxide layer to a second, greater power level used in plasma treatment of the deposited layer. The plasma treatment step is performed, in some embodiments, in a process gas consisting essentially of helium. The plasma treatment step can be performed at the same pressure as the deposition step, or at a different pressure. In one example, the plasma treatment step is performed in the same process chamber and at substantially the same pressure and temperature as the deposition step. In some embodiments the plasma is not extinguished after deposition of the silicon oxide layer and before stopping the flow of the silicon-containing precursor into the process chamber. Further, the process may include purging the process chamber to remove the silicon-containing precursor from the process chamber after the deposition of the silicon oxide and before plasma treatment.
Advantageously, the process can be performed on a substrate containing one or more layers of temperature-sensitive materials. For example, in some embodiments the deposition and plasma treatment of low-stress silicon oxide is performed on a semiconductor substrate having one or more layers of temperature-sensitive material that is sensitive to temperatures of 250° C. and higher. Examples of temperature-sensitive materials include organic materials and spin-on dielectrics.
The plasma treatment of the layer of silicon oxide reduces the content of hydrogen in the layer of silicon oxide. In some embodiments the silicon oxide obtained after plasma treatment does not have a Si—H peak at 2200-2300 cm−1 on an IR spectrum.
The described process can be implemented in a single-station or in a multi-station apparatus. In one embodiment, the method includes depositing and plasma treating a portion of the silicon oxide at a first station of a multi-station PECVD apparatus, transferring the substrate to a second station of the multi-station PECVD apparatus, and repeating depositing and plasma treating another portion of the silicon oxide in the second station of the multi-station PECVD apparatus.
The methods provided herein can be integrated with the patterning methods. In some embodiments, the processes described herein further include applying photoresist to the semiconductor substrate; exposing the photoresist to light; patterning the photoresist and transferring the pattern to the semiconductor substrate; and selectively removing the photoresist from the semiconductor substrate.
In another aspect, a method for processing a semiconductor substrate involving UV treatment is provided. The method includes: (a) providing a semiconductor substrate to a PECVD process chamber; (b) depositing a layer of silicon oxide on the semiconductor substrate by PECVD at a temperature of less than about 200° C.; (c) stopping flow of the silicon-containing precursor after deposition; and (d) treating the deposited layer of silicon oxide with UV light having a wavelength of 180 nm or less at a temperature of less than about 200° C. to modify the deposited layer and to reduce the stress of the deposited layer to an absolute value of less than about 80 MPa.
According to another aspect, an apparatus for deposition and plasma treatment of silicon oxide films is provided. The apparatus includes a PECVD process chamber, a generator configured for forming a plasma in the PECVD process chamber, and a controller. The PECVD process chamber includes a substrate support for holding the substrate in place during deposition, and one or more inlets for introducing reactants into the process chamber. The controller includes program instructions for conducting any of the deposition and plasma treatment methods provided herein.
According to another aspect, an apparatus for deposition and UV treatment of silicon oxide films is provided. The apparatus includes a PECVD process chamber, a generator configured for generating UV radiation having a wavelength of 180 nm or less in the PECVD process chamber or in a different process chamber that is dedicated for UV treatment, and a controller. The PECVD process chamber includes a substrate support for holding the substrate in place during deposition, and one or more inlets for introducing reactants into the process chamber. The controller includes program instructions for conducting any of the deposition and UV treatment methods provided herein.
According to another aspect, a system is provided herein which includes any of the apparatuses described herein and a stepper.
According to another aspect, a non-transitory computer machine-readable medium is provided, which includes program instructions for control of any of the apparatuses provided herein. The instructions include code for any of deposition and treatment methods provided herein.
These and other features and advantages of the present invention will be described in more detail below with reference to the associated drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A-1B show schematic cross sectional depictions of an exemplary semiconductor device that undergoes processing using methods provided herein.
FIG. 2 is an experimental plot of stress versus density for films deposited using low temperature PECVD without post-treatment.
FIGS. 3A-3B present process flow diagrams for silicon oxide formation processes according to embodiments provided herein.
FIG. 4 shows a schematic timing diagram for a silicon oxide formation process, according to some embodiments provided herein.
FIG. 5 is a schematic representation of a PECVD apparatus that is suitable for forming silicon oxide films in accordance with some embodiments of the present invention.
FIG. 6 is a schematic representation of one example of a multi-station apparatus suitable for forming silicon oxide films in accordance with some embodiments of the present invention.
FIG. 7 is an experimental plot of stress versus density for films deposited using low temperature PECVD with post-treatment according to embodiments provided herein.
FIG. 8 is an FT IR spectrum of a low-stress silicon oxide film obtained as provided by the embodiments disclosed herein.
FIG. 9A is an experimental plot illustrating dependence of film stress on the pressure that is used during plasma treatment of silicon oxide films provided herein.
FIG. 9B is an experimental plot illustrating dependence of film stress on the duration of plasma treatment for silicon oxide films provided herein.
FIG. 9C is an experimental plot illustrating dependence of film stress on the duration of plasma treatment for silicon oxide films of different thicknesses provided herein.



DETAILED DESCRIPTION
Introduction and Overview
Formation of high quality silicon oxide at low temperature is accomplished by depositing a silicon oxide layer by PECVD on a semiconductor substrate at a low temperature, followed by treating the deposited layer with plasma and/or UV radiation having a wavelength of less than about 180 nm to reduce the stress of deposited layer to an absolute value of less than about 80 MPa.
The terms “semiconductor substrate” and “semiconductor wafer” refer to substrates that contain semiconductor material anywhere on the substrate, and may contain layers of other materials, such as conductors and dielectrics.
The term “silicon oxide” refers to a material that is composed of silicon, oxygen, and, optionally, hydrogen. Other elements, such as carbon, nitrogen, boron and fluorine may be also present as dopants in small concentration (e.g., up to about 10% atomic excluding hydrogen). “High quality silicon oxide” refers to silicon oxide having one or any combination of the following characteristics: stress of less than about 80 MPa in absolute value; density of greater than about 2.05 g/cm3; and refractive index (RI) of less than about 1.47. In some embodiments, the high quality silicon oxide films provided herein have all of the characteristics listed above.
The term “low temperature formation” or “low temperature deposition” refers to formation of films at a temperature of less than about 200° C. In some embodiments, low temperature films are formed at a temperature of between about 100-180° C., such as between about 150-180° C.
The term “PECVD”, as used herein refers to a deposition method that involves reacting one or more molecules with plasma assistance primarily in bulk. This method is distinct from atomic layer deposition (ALD), where the reaction occurs primarily on the surface of the substrate and reactions in the bulk of the process chamber are suppressed. The term “PECVD process chamber” or “PECVD apparatus” as used herein refers to any process chamber or apparatus that is capable of conducting reactions in PECVD mode.
In general, low temperature methods of forming high-quality silicon oxide films provided herein can be used in a variety of applications, such as in logic device fabrication, in fabrication of memory devices, complementary metal-oxide-semiconductor (CMOS) image sensor devices, etc. These methods are particularly useful for applications in which several layers of material (including one or more layers of high-quality silicon oxide provided herein) are deposited in a stack on a substrate, followed by patterning of one or more layers of the stack. In some embodiments high-quality silicon oxide is deposited as part of a planar stack of at least 3 layers, of at least 5 layers, or of at least 10 layers. The combination of low stress (less than about 80 MPa, preferably less than about 50 MPa in absolute value) and low roughness (RI of less than about 1.47) is particularly advantageous for these stacking applications, since stack distortion effects would be minimized, and patterning can be performed with high precision.
In some embodiments the high-quality silicon oxide provided herein is used as a hardmask or an etch stop layer. In these embodiments, the high-quality silicon oxide is also characterized by high density (at least about 2.05 g/cm3, such as at least about 2.1 g/cm3, or such as at least about 2.15 g/cm3) in addition to low stress. Density correlates with etch selectivity, with denser materials being more resistant to etching than materials of lower density, and, therefore, high density is a particularly desirable characteristic for hardmask and etch stop applications. Hardmask layers protect the layers that lie directly underneath the hardmask from being etched, while unprotected material is etched to form recessed features. In some embodiments the high-quality silicon oxide provided herein is used as an etch stop layer. For example it can serve as an etch stop layer during etching of SiOC material that lies directly above it.
In some embodiments, the high-quality silicon oxide hardmask is deposited over a first layer (e.g., a layer of ULK dielectric), the hardmask is patterned, such that the hardmask material is removed in selected locations, exposing the first layer, and the exposed first layer is etched in the presence of the exposed hardmask. For example, a low density SiOC can be etched in a presence of exposed hardmask with a fluorine-based chemistry (e.g., using CH2F2).
Formation of silicon oxide films at low temperature is particularly desirable for substrates containing temperature-sensitive materials that can structurally or functionally deteriorate at high temperatures. In some embodiments the substrate provided for deposition of high-quality silicon oxide contains one or more layers of temperature-sensitive materials. In some embodiments this material or materials start deteriorating at 200° C. and higher, or 250° C. and higher, or 275° C. and higher. Therefore, all manipulations with these substrates should be performed at lower temperatures in order to avoid undesired deterioration of these temperature-sensitive layers. Examples of temperature-sensitive materials include organic dielectrics (which are typically deposited by spin-on methods), such as polyimide, polynorbornenes, and benzocyclubutene-based polymers.
FIG. 1A illustrates a cross-sectional schematic view of an example of a semiconductor substrate 100 before formation of a high-quality silicon oxide layer. The substrate contains a layer of ultra low-k (ULK) dielectric 101, where the ULK dielectric has a dielectric constant of about 2.2 or less. The ULK dielectric can be deposited by CVD, PECVD, or a spin-on method on an underlying layer (not shown). In some embodiments the ULK dielectric is a porous dielectric that includes silicon and oxygen. The ULK layer may reside over an underlying metallization layer that may include another layer of ULK dielectric having embedded metal lines. Layer 103 resides over and in contact with the ULK dielectric layer 103, and in the illustrated embodiment is a temperature-sensitive layer containing organic spin-on dielectric that is susceptible to degradation at temperatures that are used in conventional PECVD (e.g., at 250° C. and higher or 300° C. and higher).
FIG. 1B illustrates a cross-sectional schematic view of the semiconductor substrate 100 after deposition of the high-quality silicon oxide hardmask 105. The hardmask 105 is formed using low-temperature methods provided herein over and in contact with the spin-on dielectric layer 103. In some embodiments, the thickness of the formed hardmask is between about 100-200 Å. After formation of the hardmask layer 105 one or more planar layers may be deposited over the hardmask layer 105, forming a stack of at least 3, or at least 5 layers. In some embodiments, one of these overlying layers is a photoresist layer, which is then patterned, and the pattern is transferred to the hardmask layer 105 using photolithographic techniques. The patterning can remove portions of high-quality silicon oxide material in selected locations, exposing the underlying layer 103. Then, exposed layer 103 (and subsequently exposed ULK dielectric layer 101) can be etched in a presence of exposed hardmask 105. In some embodiments, the semiconductor processing methods include etching a layer of material that underlies or overlies the layer of high quality silicon oxide, in the presence of exposed silicon oxide, where the silicon oxide serves as a hardmask or an etch stop layer.
Prior to development of methods provided herein, formation of low-stress silicon oxide at low temperature using PECVD presented an unsolved problem, because it was not possible to lower the stress of PECVD films to less than 120 MPa in absolute value using variation of PECVD parameters, such as pressure, process gas composition, and power used in plasma generation. Films with stresses in excess of 100 MPa have limited utility, particularly in applications that involve patterning, and therefore new PECVD-based methods for producing high quality silicon oxide at low temperature were needed.
FIG. 2 shows an experimental plot illustrating stress and density for silicon oxide films deposited by conventional PECVD at 180° C. The films were deposited on a 300 mm wafer using a mixture of SiH4, CO2 and He as a process gas. The plasma was formed using high frequency (HF) plasma generation at 13.56 MHz, and the power used for plasma generation varied between 100 W and 400 W for different films. The deposition pressure was varied between 2.5 Torr and 5 Torr for different films, and the composition of the process gas varied in CO2/SiH4 ratio between 100 and 200 for different films. It can be seen from the plot that all deposited films had compressive stress in excess of 120 MPa in absolute value and the density ranged from about 2.01 to about 2.14 g/cm3. The density and film stress behaved as independent parameters in this study.
A method for dramatically reducing the stress of silicon oxide films to less than about 80 MPa, such as to less than about 50 MPa, or even to less than about 30 MPa has been unexpectedly discovered. The method involves, according to one aspect, treating the silicon oxide that was deposited by low temperature PECVD, with a plasma (such as with helium plasma) to thereby modify the silicon oxide layer and to reduce the stress of the formed layer to less than about 80 MPa in absolute value. In another aspect, the method involves treating the silicon oxide that was deposited by low temperature PECVD, with a UV radiation having a wavelength of less than about 180 nm to thereby modify the silicon oxide layer and reduce the stress of the formed layer to less than about 80 MPa in absolute value.
Methods for Forming Low Stress Silicon Oxide Films
Methods for forming low stress silicon oxide films at low temperature are illustrated in process flow diagrams shown in FIG. 3A and in FIG. 3B. Referring to FIG. 3A, the process starts in 301 by providing a substrate to a PECVD process chamber. The substrate is typically a semiconductor substrate. In some embodiments the substrate is a planar substrate that contains one or more layers of temperature-sensitive materials, as illustrated in FIG. 1A. The PECVD process chamber is configured for conducting reactions in a PECVD mode, and typically includes a support for holding the substrate in place during deposition, one or more inlets for introducing the reactants (such as a silicon-containing precursor, and an oxygen-containing reactant) and an outlet for removing one or more gases from the process chamber. The process chamber, in some embodiments, is equipped with a heater configured to heat the substrate during the deposition. The apparatus that contains the process chamber is configured for generating a plasma in the process chamber and conducting reactions in PECVD mode. The PECVD process chamber may also have the capability of conducting reactions in different modes, but is referred to as a “PECVD process chamber” when it is used to conduct PECVD reactions. For example a plasma enhanced atomic layer deposition (PEALD) process chamber, when used to conduct reactions in PECVD mode, is a “PECVD process chamber” as used herein.
After the substrate has been provided to the PECVD process chamber, in 303, a layer of silicon oxide is deposited by PECVD at a temperature of less than about 200° C. The deposition process involves providing a silicon-containing precursor and an oxygen-containing reactant to the process chamber and forming a plasma in the process chamber. Examples of suitable silicon-containing precursors include carbon-free precursors, e.g., silane (SiH4), disilane (Si2H6), trisialne (Si3H8), and dichlorosilane (SiH2Cl2); and carbon-containing precursors, such as alkoxysilanes, alkylsilanes, cyclic siloxanes, alkynylsilanes, and orthosilicates (e.g., tetraethylorthosilicate). Examples of suitable oxygen-containing reactants include O2, CO2, and N2O. When the silicon-containing precursor includes both silicon and oxygen (e.g., tetraethylorthosilicate), such single precursor may be used both as a silicon source and as an oxygen-containing reactant. The deposition process gas containing the silicon-containing precursor and the oxygen-containing reactant is typically flowed into the process chamber (in some cases with prior vaporization of liquid reactants) together with a diluent gas that is, in some embodiments, an inert gas that is not participating in the PECVD reaction. Examples of diluent gases include N2 and noble gases, such as helium, argon, neon, and krypton.
The temperature is maintained at less than about 200° C. during the deposition process. In some embodiments the deposition temperature is 180° C. or less. For example, films can be deposited at a temperature of between about 100-180° C. The pressure during deposition can vary, and in some embodiments is between about 1-10 torr, more preferably between about 1.5-5 torr, such as about 3.5 torr. The flow rates of individual components of the process gas depend on the size of the process chamber and can be in the range of between about 10-10,000 sccm, in some embodiments. In some embodiments the ratio of the flow rate of an oxygen-containing reactant to the flow rate of the silicon-containing precursor is less than about 300, such as about 200. In one example the ratio of the flow rate of CO2 to the flow rate of SiH4 is less than about 300.
The deposition is performed in some embodiments using only high frequency radio frequency (HF RF) plasma generation (single-frequency deposition). In other embodiments both high frequency and low frequency radio frequency (LF RF) plasma generation are used (dual frequency deposition). HF plasma is generated using frequencies of between about 1.8 MHz and 2.45 GHz, such as at 13.56 MHz. Low frequency plasma is generated using frequencies of between about 50 kHz and 900 kHz, such as 400 kHz. In some embodiments, deposition of silicon oxide is performed using a relatively low power in single frequency HF deposition. For example, the power used for generation of plasma can be in the range of about 100-500 W for deposition on a single 300 mm wafer, corresponding to the power density of between about 0.14 W/cm2 to about 0.71 W/cm2.
Deposition is performed until a desired amount of silicon oxide is formed on the substrate. In some embodiments a silicon oxide layer having a thickness of about 100-200 Å is deposited in a single step. In other embodiments, a portion of silicon oxide is deposited, and treated, and the process is repeated until a desired thickness of silicon oxide has been achieved.
Silicon oxide films immediately after deposition typically have low quality, and are characterized by relatively high hydrogen content and high stress. The IR spectrum of such films exhibits a prominent Si—H peak at about 2250 cm−1, and the stress values are typically in excess of 100 MPa in absolute value (films are compressive).
After these low-quality films have been deposited by low temperature PECVD, in operation 305 the deposited films are treated with a plasma in an absence of the silicon-containing precursor to reduce the stress of deposited films to less than about 80 MPa in absolute value. In some embodiments the flows of the silicon-containing precursor and of the oxygen-containing reactant are stopped after the silicon oxide film has been deposited, and the residual silicon containing precursor is removed from the process chamber by purging and/or evacuation. Next, a plasma treatment process gas, such as helium is provided into the process chamber, and the substrate is treated with a plasma. In some embodiments the plasma treatment is performed in a plasma treatment process gas consisting essentially of helium.
The deposition operation 303 and the treatment operation 305 can be advantageously performed in the same PECVD process chamber. In some embodiments, plasma is not extinguished after the deposition is completed and is maintained throughout the deposition, the purging and the plasma treatment steps. In other embodiments plasma may be extinguished after the deposition has been completed, and then re-ignited during plasma treatment. In yet other embodiments, plasma treatment 305 and silicon oxide deposition 303 are performed in different process chambers, or even in different apparatuses. In one of the preferred embodiments, the plasma treatment is performed shortly after the deposition is completed, such as within about 5 minutes or within 1 minute after deposition has been completed.
In some embodiments (particularly when deposition 303 and treatment 305 are performed in a single chamber without a vacuum break), the plasma treatment process gas (e.g. helium) is the same gas as the diluent gas used during deposition 303, and during purging of the process chamber after 303. In some embodiments the flow rate of the plasma treatment gas (e.g., helium) during plasma treatment is at least 1.5 times, such as at least 2 times greater than the flow rate of the diluent gas during deposition. For example, in some embodiments helium flow rate (as a diluent gas) during deposition 303 is about 1000 sccm, and this flow rate is increased to about 2500 in the plasma treatment step 305, where helium is used as the plasma treatment process gas. Further, the power used for plasma generation is greater during the plasma treatment step 305 than during the deposition step 303. In some embodiments the power used during the plasma treatment step is at least 2 times greater, such as at least 3 times greater than the power used during the deposition step.
The temperature during the plasma treatment step is preferably maintained at less than about 200° C., such as at 100-180° C. The pressure during plasma treatment ranges in some embodiments between about 1-10 torr, such as between about 1-5 torr. In some embodiments the temperature and pressure during the deposition step 303 is the same as the temperature and pressure during the plasma treatment 305. In other embodiments only one of these parameters is kept constant. The use of same pressure and/or temperature during deposition 303 and plasma treatment 305 increases the overall stability of the process.
The duration of the plasma treatment is typically in the range of between about 6 and 20 seconds and is one of parameters that can be changed to tune the stress of the formed silicon oxide layers.
Another aspect of the invention is a method for tuning the stress of silicon oxide to a desired level. The method involves modulating one or more parameters selected from the group consisting of plasma treatment pressure, plasma treatment duration, and power level used in plasma generation during plasma treatment.
Without wishing to be bound by a particular theory of operation, it is suggested that the improvement in stress obtained after helium plasma treatment is observed, at least in part, as a result of interaction between UV radiation formed in a helium plasma and the deposited silicon oxide layer. The UV radiation formed in a helium plasma has wavelength of less than 180 nm. In another aspect of the invention, a method is provided for forming high quality silicon oxide at low temperature using UV radiation having a wavelength of less than about 180 nm. The process flow diagram for this method is presented in FIG. 3B. The steps 307 and 309 are identical to the steps 301 and 303 shown in FIG. 3A. After the silicon oxide layer has been deposited by low temperature PECVD, the silicon oxide layer is treated in 311 with UV radiation having wavelength of less than about 180 nm to reduce the stress of the silicon oxide layer to less than 80 MPa in absolute value. The UV treatment is preferably performed at a temperature of less than 200° C. Suitable sources of UV radiation include sources that utilize excitation (as in a plasma) of H, He, Ar, O2, etc.
A specific example of a process that uses helium plasma treatment for reducing stress of a PECVD silicon oxide is illustrated in FIG. 4. FIG. 4 provides a timing diagram that schematically illustrates the flow rates of the components of the process gases, and plasma power levels during the deposition step 401, the purge step 403, and the plasma treatment step 405. It is understood that the diagram is not drawn to scale and provides a general overview of the process. In step 401, the process gas consisting essentially of SiH4, CO2 and He is provided to the process chamber and silicon oxide is deposited using HF RF plasma formed in the process gas using 13.56 MHz frequency and a first power level.
Specific process conditions for the deposition step 401 are provided in Table 1. The parameters are provided for deposition on a single 300 mm wafer substrate and it is understood that plasma power levels and flow rates can be scaled to any desired substrate or a plurality of substrates. For example, when four wafers are processed simultaneously in an apparatus having four processing stations, plasma power and flow rates of gasses should be four times greater than those listed in the Tables 1-3.







TABLE 1







Deposition of silicon oxide on a 300 mm substrate.









Parameter
Range
Example





Temperature, ° C.
100-199° C.
180° C.


Pressure, torr
1.8-5 Torr
3.5 Torr


HF RF plasma power, W
100-2000 W
400 W


SiH4 flow rate, sccm
5-100 sccm
30 sccm


CO2 flow rate, sccm
1000-10000 sccm
4200 sccm


He flow rate, sccm
100-10000 sccm
1250 sccm


CO2/SiH4 flow rate ratio
Less than 300
140


Duration, seconds
1-100 s
5 s









Next, in the purge step 403, only helium is flowed into the process chamber and it purges the silane and carbon dioxide out of the process chamber. The plasma is not extinguished during this step, and plasma power is not changed. Table 2 lists the process parameters used during the purging step 403.







TABLE 2







Purging after deposition of silicon oxide on a 300 mm substrate.









Parameter
Range
Example





Temperature, ° C.
100-199° C.
180° C.


Pressure, torr
1.8-5 Torr
3.5 Torr


HF RF plasma power, W
100-2000 W
500 W


SiH4 flow rate, sccm
0 sccm
0 sccm


CO2 flow rate, sccm
0 sccm
0 sccm


He flow rate, sccm
100-10000 sccm
1000 sccm


CO2/SiH4 flow rate ratio
Not applicable
Not applicable


Duration, seconds
0.5-20s
5s









After the purge is completed, the deposited silicon oxide film is treated with a helium plasma in step 405. During this step, the plasma power and the helium flow rate are increased. Table 3 lists the process parameters for the plasma treatment step.







TABLE 3







Plasma treatment of silicon oxide on a 300 mm substrate.











Parameter
Range
Example







Temperature, ° C.
100-199° C.
180° C.



Pressure, torr
1.8-5 Torr
3.5 Torr



HF RF plasma power, W
500-1200 W
1000 W



SiH4 flow rate, sccm
0 sccm
0 sccm



CO2 flow rate, sccm
0 sccm
0 sccm



He flow rate, sccm
100-10000 sccm
2500 sccm



CO2/SiH4 flow rate ratio
Not applicable
Not applicable



Duration, seconds
0.5-50 seconds
6 seconds










Apparatus
The present invention can be implemented in many different types of apparatus that allow deposition of silicon oxide in PECVD mode. Generally, the apparatus will include one or more chambers or “reactors” (sometimes including multiple stations) that house one or more wafers and are suitable for wafer processing. Each chamber may house one or more wafers for processing. The one or more chambers maintain the wafer in a defined position or positions (with or without motion within that position, e.g. rotation, vibration, or other agitation). In one embodiment, a wafer undergoing the deposition and plasma treatment is transferred from one station to another within the reactor during the process. For example in some implementations, a portion of silicon oxide is deposited on a wafer by PECVD and is plasma treated at a first station of the PECVD apparatus; the wafer is then transferred to a second station of the PECVD apparatus, where an addition portion of silicon oxide is deposited by PECVD and is treated. In one embodiment, formation of a high-quality silicon oxide layer of a desired thickness is deposited in four stations, where each station deposits and treats one fourth of the layer thickness. For example if a 100 Å is the target thickness of the layer, each station deposits and treats 25 Å thick silicon oxide film.
While in process, each wafer is held in place by a pedestal, wafer chuck and/or other wafer holding apparatus. For certain operations in which the wafer is to be heated, the apparatus may include a heater such as a heating plate. In one embodiment of the invention, a PECVD system is used both for deposition and treatment of the layer. When treatment is UV treatment, the source of UV radiation with a wavelength of less than 180 nm can be incorporated into the PECVD apparatus. In other embodiments, separate process chambers or even separate apparatuses may be used for the deposition and treatment steps.
FIG. 5 provides a simple block diagram depicting various PECVD reactor components arranged for implementing the present invention. As shown, a reactor 500 includes a process chamber 524, which encloses other components of the reactor and serves to contain the plasma generated by a capacitor type system including a showerhead 514 working in conjunction with a grounded heater block 520. A high-frequency RF generator 502 and an optional low-frequency RF generator 504 are connected to a matching network 506 that, in turn is connected to showerhead 514.
Within the reactor, a wafer pedestal 518 supports a substrate 516. The pedestal typically includes a chuck, a fork, or lift pins to hold and transfer the substrate during and between the deposition reactions. The chuck may be an electrostatic chuck, a mechanical chuck or various other types of chuck as are available for use in the industry and/or research.
The process gases are introduced via inlet 512. Multiple source gas lines 510 are connected to manifold 508. The gases may be premixed or not. Appropriate valving and mass flow control mechanisms are employed to ensure that the correct gases are delivered during the deposition, purging, and plasma treatment, phases of the process. In case the chemical precursor(s) is delivered in the liquid form, liquid flow control mechanisms are employed. The liquid is then vaporized and mixed with other process gases during its transportation in a manifold heated above its vaporization point before reaching the deposition chamber.
Process gases exit chamber 500 via an outlet 522. A vacuum pump 526 (e.g., a one or two stage mechanical dry pump and/or a turbomolecular pump) typically draws process gases out and maintains a suitably low pressure within the reactor by a close loop controlled flow restriction device, such as a throttle valve or a pendulum valve.
A controller 530 is associated with the PECVD reactor 500 and can include program instructions for performing any of the processes described herein. For example the controller 530 can specify the necessary parameters for performing deposition of the PECVD silicon oxide at low temperature, for purging the process chamber to remove a silicon-containing precursor, and for plasma treating the deposited silicon oxide layer to reduce the stress of the silicon oxide layer.
In one of the embodiments a multi-station apparatus may be used for PECVD deposition and treatment. The multi-station reactor allows one to run different processes concurrently in one chamber environment, thereby increasing the efficiency of wafer processing. One example of such an apparatus is depicted in FIG. 6. A schematic presentation of top view is shown. An apparatus chamber 601 comprises four stations 603-609. In general, any number of stations is possible within the single chamber of a multi-station apparatus. Station 603 is used for loading and unloading of the substrate wafers. An indexing plane 611 is used to index wafers from station to station. A controller 613 can comprise instructions for the processes described herein. Stations 603-609 may have the same or different functions. For example, some of the stations may be devoted to PECVD deposition, while others may be used only for plasma treatment of deposited films. In one of the embodiments, individual stations can operate under distinct process conditions and may be substantially isolated from each other. In another implementation, each station is configured to perform PECVD deposition and treatment of the deposited layer.
According to one of the embodiments described above, all stations 603-609 are configured to perform the same function, and each station is configured for both PECVD deposition of silicon oxide and for treatment of deposited layer. An indexing plate 611 is used to lift the substrates off the pedestals and to accurately position the substrates at the next processing station. After the wafer substrate is loaded at station 603, it is indexed to station 605, where formation of the high quality silicon oxide film (including PECVD deposition and treatment) is performed. The wafer is then moved to station 607 where and additional portion of silicon oxide is deposited and treated. The substrate is further indexed to station 609, where further deposition and treatment of silicon oxide is performed, and then indexed to station 603 to deposit and treat more of diffusion silicon oxide layer. For example, each station may deposit and treat 25 Å of silicon oxide to form a 100 Å thick silicon oxide layer, or each station may deposit and treat 50 Å of silicon oxide to form a 200 Å thick silicon oxide layer. The processed wafer is unloaded at station 603, and the module is charged with a new wafer. During normal operation, a separate substrate occupies each station and each time the process is repeated the substrates are moved to new stations. Thus, an apparatus having four stations 603, 605, 607, and 609 allows simultaneous processing of four wafers. This type of processing that involves breaking down the film formation into substantially identical phases, where each phase includes deposition and treatment of a portion of the film, is particularly advantageous because it increases wafer-to wafer reproducibility of deposition.
The process conditions and the process flow itself can be controlled by a controller unit 613 which comprises program instructions for a monitoring, maintaining and/or adjusting certain process variables, such as RF plasma power, gas flow rates and times, temperature, pressure and the like. For example, instructions specifying flow rates of silane and CO2 for silicon oxide deposition may be included. The instructions may specify all of the parameters to perform operations, according to methods described above. For example, instructions may include parameters of PECVD deposition, purging, and plasma treatment. The controller may comprise different or identical instructions for different apparatus stations, thus allowing the apparatus stations to operate either independently or synchronously.
In some implementations, a controller is part of a system, which may be part of the above-described examples. Such systems can comprise semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and/or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The controller, depending on the processing requirements and/or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and/or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and/or load locks connected to or interfaced with a specific system.
Broadly speaking, the controller may be defined as electronics having various integrated circuits, logic, memory, and/or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and/or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some embodiments, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and/or dies of a wafer.
The controller, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing steps to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and/or settings, which are then communicated to the system from the remote computer. In some examples, the controller receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus as described above, the controller may be distributed, such as by comprising one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.
Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an atomic layer deposition (ALD) chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and/or manufacturing of semiconductor wafers.
As noted above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and/or load ports in a semiconductor manufacturing factory. Machine-readable media containing instructions for controlling process operations in accordance with the present invention may be coupled to the system controller.
The apparatus/process described hereinabove may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels and the like. Typically, though not necessarily, such tools/processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically comprises some or all of the following steps, each step enabled with a number of possible tools: (1) application of photoresist on a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or workpiece by using a dry or plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.
Several embodiments of the described methods and devices will now be illustrated by specific examples.
EXPERIMENTAL EXAMPLES
Example 1. Formation of Silicon Oxide Films Having Low Stress and High Density
A number of silicon oxide films were deposited by PECVD in a Vector PECVD reactor available from Lam Research Corporation, Fremont Calif., on planar 300 mm wafers at a temperature of 180° C., and pressures of 2.5 Torr-3.5 Torr. The process gas used during deposition consisted of SiH4 (provided at 30 sccm), CO2 (provided at 4200 sccm) and He. Plasma was generated in the process gas using HF RF generation at 13.56 MHz at a power level of 100-400 W. The deposition was conducted for 5 seconds; then the flows of SiH4 and CO2 into the process chamber were stopped, while the plasma and helium flow remained on for 5 seconds to purge the SiH4 and CO2 out of the process chamber. Next, plasma power was increased to 500-1000 W and helium flow was increased to 1000-4000 sccm and the deposited silicon oxide films were plasma treated under these conditions for 6-20 seconds. Temperature and pressure remained constant for each film throughout the process. The flow rates and plasma power levels are given for processing on a single wafer. The films were deposited to a thickness of 400 Å in order to facilitate accurate measurement of stress. After deposition, stress and density of the formed films were measured. Stress was calculated using a measurement of the bow change of the Si wafer substrate and the film thickness ellipsometry. Density was calculated by the change in mass on the Si substrate and the film thickness ellipsometry. The density and stress values of formed films are illustrated in the plot shown in FIG. 7. It can be seen that films with absolute stress values of less than 80 MPa, and even less than 50 MPa were obtained. Some films exhibited stress values of less than 30 MPa. The formed films have densities of greater than 2.05 g/cm3. Some films have densities of greater than 2.1 g/cm3. It can be seen from FIG. 7 that there is a correlation between the density and stress trends, as lower stress (in absolute value) is associated with lower density. Nevertheless, provided methods produce films that have acceptable stress and density values that are suitable for hardmask applications. In contrast, in the absence of plasma treatment, PECVD silicon oxide films that are formed at low temperature had absolute stress values in excess of 100 MPa
Example 2. Structure of Formed Low-Stress Films
An FT IR spectrum of a low-stress silicon oxide material was obtained. The film was formed as described in Example 1, using the following process parameters: temperature of 180° C., pressure of 3.5 Torr, plasma power of 100 W (generated at 13.56 Mhz), SiH4 flow rate of 30 sccm, CO2 flow rate of 4200 sccm and He flow rate of 1250 sccm. The formed film had a stress of less than −40 MPa. It can be seen that the FT IR spectrum does not have a Si—H peak at about 2250 cm−1, which is typically present in silicon oxide films deposited by low temperature PECVD without plasma post-treatment. This indicates that plasma post-treatment reduces the concentration of hydrogen in the formed films.
Example 3. Improvement of Stress, Density, and RI by Plasma Post-Treatment
A comparative silicon oxide film was deposited by low temperature PECVD to a thickness of 411 Å, and its stress, density and RI were measured. The deposition was conducted at a temperature of 180° C., and pressure of 3.5 Torr, using plasma power of 100 W (13.56 Mhz), SiH4 flow rate of 30 sccm, CO2 flow rate of 4200 sccm and He flow rate of 1250 sccm.
Another silicon oxide film was deposited by low temperature PECVD using the same process conditions as those used in the deposition of the comparative film above, and was then plasma treated at a temperature of 180° C., pressure of 3.5 Torr, using plasma power of 500 W (13.56 Mhz), and He flow rate of 1000 sccm. Stress, density, and RI of the treated film were measured.
Parameters for the comparative film and for the treated film are provided in Table 4.







TABLE 4







Improvement of stress, density, and RI upon plasma treatment.











Parameter
Comparative Film
Treated Film















Stress (compressive MPa)
137
11



Density (g/cm3)
2.03
2.13



RI (n @ 633 nm)
1.505
1.500










It is noted that RI of greater than 1.47 was obtained due to a metrology offset for thin films. RI was measured using ellipsometry.
Example 4. Modulation of Stress Using Pressure in the Treatment Step
Four films were deposited and treated with helium plasma as described in Example 1. The following conditions were used: temperature of 180° C., plasma power of 100 W (13.56 MHz), SiH4 flow rate of 30 sccm, CO2 flow rate of 4200 sccm and He flow rate of 1250 sccm. The pressure during deposition was constant for all four films and was 3.5 Torr. Pressure during plasma treatment step was varied between 1.5 torr, 2.5 torr, 3.5 torr and 4.5 torr. Treatment pressure was the only process parameter that was varied during film formation. FIG. 9A provides a plot of stress values for the four films as a function of treatment pressure. It can be seen that the absolute value of stress was reduced with the increasing pressure from about 50 Mpa to about 35 MPa.
Example 5. Modulation of Stress Using Plasma Treatment Time
Several films having different thicknesses were deposited and plasma treated with helium as described herein. The effect of duration of plasma treatment step on film stress was studied and is shown in FIG. 9B. 50 Å films (curve a) exhibited reduction in stress from about 50 MPa to about 10 MPa in absolute value as duration of treatment was increased from 3 seconds to 12 seconds. 33 Å films (curve b) and 25 Å films (curve c) were somewhat less responsive to changes in treatment duration time.
Example 6. Modulation of Stress Using Plasma Treatment Time for Films of Different Thicknesses
Several films having different thicknesses were deposited and plasma treated with helium as described herein. The effect of duration of plasma treatment step on film stress was studied and is shown in FIG. 9C. 50 Å films (curve a) treated using 500 W plasma power exhibited a decrease in absolute stress as duration of treatment was increased from 6 seconds to 12 seconds. Films having 100 Å thickness (curve b) treated using 500 W plasma power also exhibited a decrease in stress as duration of treatment was increased from 12 seconds to 20 seconds.
Although various details have been omitted for clarity's sake, various design alternatives may be implemented. Therefore, the present examples are to be considered as illustrative and not restrictive, and the invention is not to be limited to the details given herein, but may be modified within the scope of the appended claims.

## Claims

1. A method for processing a semiconductor substrate, the method comprising:
(a) providing a semiconductor substrate to a PECVD process chamber;
(b) depositing a layer of silicon oxide on the semiconductor substrate by PECVD at a temperature of less than about 200° C., wherein the depositing comprises flowing a silicon-containing precursor and an oxygen-containing reactant into the PECVD process chamber and forming a plasma;
(c) stopping flow of the silicon-containing precursor after deposition; and
(d) treating the deposited layer of silicon oxide with a plasma at a temperature of less than about 200° C. to thereby modify the deposited layer and to reduce the stress of the deposited layer to an absolute value of less than about 80 MPa.

2. The method of claim 1, wherein the method comprises increasing power that is used for plasma generation from a first power level used in (b) to a second, greater power level used in (d).

3. The method of claim 1, wherein (d) comprises treating the deposited layer of silicon oxide with a plasma formed in a process gas consisting essentially of helium.

4. The method of claim 1, wherein the semiconductor substrate provided in (a) comprises one or more layers of temperature-sensitive material that is sensitive to temperatures of 250° C. and higher.

5. The method of claim 4, wherein the temperature-sensitive material is an organic material.

6. The method of claim 4, wherein the temperature-sensitive material is a spin-on dielectric.

7. The method of claim 1, wherein the deposition of the layer of silicon oxide is performed at a temperature of less than about 180° C.

8. The method of claim 1, wherein the absolute value of stress of the silicon oxide layer obtained after (d) is less than about 50 MPa.

9. The method of claim 1, wherein the absolute value of stress of the silicon oxide layer obtained after (d) is less than about 10 MPa.

10. The method of claim 1, wherein the plasma treatment of the layer of silicon oxide in (d) reduces the content of hydrogen in the layer of silicon oxide.

11. The method of claim 1, wherein the silicon oxide obtained after plasma treatment in (d) does not have a Si—H peak at 2200-2300 cm−1 on an IR spectrum.

12. The method of claim 1, wherein the method comprises maintaining the plasma after (b) and before (c).

13. The method of claim 1, further comprising purging the PECVD process chamber after (b) and before (d) to remove the silicon-containing precursor from the process chamber.

14. The method of claim 1, wherein (b) further comprises flowing an inert gas into the PECVD process chamber.

15. The method of claim 14, wherein the silicon-containing precursor is SiH4, the oxygen-containing reactant is CO2 and the inert gas is He.

16. The method of claim 1, wherein (b) is performed at a pressure of between about 1.5-5 Torr.

17. The method of claim 1, wherein (b) and (d) are performed in the same PECVD process chamber at substantially the same pressure and temperature.

18. The method of claim 1, wherein (b)-(d) are performed at a first station of a multi-station PECVD apparatus, wherein the method further comprises transferring the semiconductor substrate to a second station of a multi-station PECVD apparatus after (d), and repeating (b)-(d) in the second station of the multi-station PECVD apparatus.

19. The method of claim 1, further comprising:
applying photoresist to the semiconductor substrate;
exposing the photoresist to light;
patterning the photoresist and transferring the pattern to the semiconductor substrate; and
selectively removing the photoresist from the semiconductor substrate.

20. A method for processing a semiconductor substrate, the method comprising:
(a) providing a semiconductor substrate to a PECVD process chamber;
(b) depositing a layer of silicon oxide on the semiconductor substrate by PECVD at a temperature of less than about 200° C.;
(c) stopping flow of the silicon-containing precursor after deposition; and
(d) treating the deposited layer of silicon oxide with UV light having a wavelength of 180 nm or less at a temperature of less than about 200° C. to modify the deposited layer and to reduce the stress of the deposited layer to an absolute value of less than about 80 MPa.