US20080176390A1 - Method of forming carbon-containing silicon nitride layer - Google Patents

Method of forming carbon-containing silicon nitride layer Download PDF

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US20080176390A1
US20080176390A1 US12/055,323 US5532308A US2008176390A1 US 20080176390 A1 US20080176390 A1 US 20080176390A1 US 5532308 A US5532308 A US 5532308A US 2008176390 A1 US2008176390 A1 US 2008176390A1
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carbon
silicon nitride
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Po-Lun Cheng
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United Microelectronics Corp
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    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02167Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • H01L21/02205Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
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Abstract

A method for forming a carbon-containing silicon nitride layer with superior uniformity by low pressure chemical vapor deposition (LPCVD) using disilane, ammonia and at least one carbon-source precursor as reactant gases is provided.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This application is a continuation application of the prior field application Ser. No. 11/531,283, filed Sep. 13, 2006. The prior field application Ser. No. 11/531,283 claims the priority benefit of U.S. provisional application Ser. No. 60/716,848, filed on Sep. 13, 2005. The entirety of the above-mentioned patent application is hereby incorporated by reference herein and made a part of this specification.
  • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention generally relates to a method of forming a semiconductor device. More particularly, the present invention relates to a method for forming a carbon-containing silicon nitride layer.
  • 2. Description of Related Art
  • The metal-oxide-semiconductor (MOS) field effect transistor is the most important device applied for ultra-large-integrated-circuits, such as microprocessors and semiconductor memories. The MOSFET transistor generally includes a conductive gate structure and a source/drain region disposed on both sides of the gate structure. To increase the number of components per IC chip, the device dimensions must be scaled down. As the device dimension shrinks, the channels become shorter, thus inducing undesirable short channel effects. In the prior art, the source/drain region is coupled with a lightly doped drain (LDD) structure for preventing short channel effect and hot carrier effects.
  • During the fabrication of the MOSFET, after forming the gate electrode, the offset spacer and/or the spacer, made of silicon oxide or silicon nitride, will be formed on the two sidewalls of the gate electrode in the subsequent processes. Afterwards, ion implantation will be performed to form the LDD structure or the source and drain regions at the two sides of the gate electrode, through the offset spacer or the spacer. For example, a composite silicon oxide/silicon nitride spacer may be formed on the sidewalls of the gate by forming an offset oxide layer and a silicon nitride layer covering the substrate and the gate electrode in sequence and then performing etching to remove a portion of the silicon nitride layer until the offset oxide layer is exposed. During the ion implantation process, the uniformity of the oxide or nitride layer of the offset spacer or the spacer has great impact on the dopant profile or junction profile of the formed LDD structure or even the source/drain region.
  • However, when the size of the device and the line-width shrink, the thickness of each layer and the process margin in each layer also become smaller. Especially if the offset spacer or spacer is made from a non-uniform silicon nitride layer, not only the junction depth of the subsequent doped regions region may be diverse, the effective channel length of the gate electrode may also be changed, which significantly affects the reliability and uniformity of the semiconductor devices on the wafer.
  • SUMMARY OF THE INVENTION
  • Accordingly, the present invention is directed to a method for forming a carbon-containing silicon nitride layer with superior uniformity, by low pressure chemical vapor deposition (LPCVD) using disilane, ammonia and at least one carbon-source precursor as reactant gases. Moreover, the carbon content of the formed carbon-containing silicon nitride layer can be higher than 9%.
  • The present invention is also directed to a method for forming a gate structure, by forming offset spacers and spacers including at least a carbon-containing silicon nitride layer of superior uniformity and high carbon content. Therefore, the performance of the device can be enhanced.
  • The present invention provides a method for forming a gate structure. After forming the gate electrode on the provided substrate, offset spacers are formed on the sidewalls of the gate electrode, the material of the offset spacers is carbon-containing silicon nitride. Thereafter, a material layer is formed over the substrate and covering the gate electrode. The material layer includes at least a carbon-containing silicon nitride layer formed by low pressure chemical vapor deposition (LPCVD). Subsequent to etching back the material layer, spacers are formed over sidewalls of the gate electrode.
  • According to an embodiment of the method for forming a gate, the carbon-containing silicon nitride layer has a carbon content higher than 9%.
  • According to an embodiment of the method for forming a gate, the carbon-containing silicon nitride layer has a carbon content ranging from about 9% to about 30%.
  • According to an embodiment of the method for forming a gate, the carbon-containing silicon nitride layer is formed by a single wafer tool.
  • According to an embodiment of the method for forming a gate, the carbon-containing silicon nitride layer is formed by using reactant gases including at least a carbon-source precursor, and the carbon-source precursor is selected from the group consisting of TEASAT (triethylarsenate, C6H15AsO4), Trans-LC (C2H2Cl2), TCS (trichlorosilane, SiHCl3), TMAl (trimethyl aluminum, Al(CH3)3), C2H, C3H6, TEB (triethylborate, B(OC2H5)3), TEPO (triethylphosphate, PO(C2H5O)3), TDMAT (tetrakis-dimethylamino titanium, Ti[N(CH3)2]4) and combinations thereof.
  • According to an embodiment of the method for forming a gate, a gas flow rate of the carbon-source precursor is less than 2 slm (standard liter per minute).
  • According to an embodiment of the method for forming a gate, a reaction pressure of the LPCVD for forming the carbon-containing silicon nitride layer is below 250 Torr. A reaction temperature of the LPCVD for forming the carbon-containing silicon nitride layer is below 800° C.
  • According to an embodiment of the method for forming a gate, the step of forming the offset spacers comprises: forming a carbon-containing silicon nitride offset material layer over the substrate; and etching back the carbon-containing silicon nitride offset material layer to form the offset spacers on the sidewalls of the gate electrode.
  • According to an embodiment of the method for forming a gate, the carbon-containing silicon nitride offset material layer is formed by low pressure chemical vapor deposition (LPCVD) using disilane, ammonia and at least a carbon-source precursor as reactant gases. The carbon-source precursor is selected from the group consisting of TEASAT (triethylarsenate, C6H15AsO4), Trans-LC (C2H2Cl2), TCS (trichlorosilane, SiHCl3), TMAl (trimethyl aluminum, Al (CH3)3), C2H4, C3H6, TEB (triethylborate, B(OC2H5)3), TEPO (triethylphosphate, PO(C2H5O)3), TDMAT (tetrakis-dimethylamino titanium, Ti[N(CH3)2]4) and combinations thereof.
  • According to an embodiment of the method for forming a gate, a reaction pressure of the LPCVD for forming the carbon-containing silicon nitride offset material layer is below 250 Torr. A reaction temperature of the LPCVD for forming the carbon-containing silicon nitride offset material layer is below 800° C.
  • According to an embodiment of the method for forming a gate, the carbon-containing silicon nitride offset material layer has a carbon content higher than 9%.
  • According to an embodiment of the method for forming a gate, the carbon-containing silicon nitride offset material layer has a carbon content ranging from about 9% to about 30%.
  • According to an embodiment of the method for forming a gate, the carbon-containing silicon nitride offset material layer is formed by a single wafer tool.
  • According to the method for forming the carbon-containing silicon nitride layer proposed in this invention, the carbon-containing silicon nitride layer can offer better superior uniformity and high carbon content, when compared with the conventional silicon nitride layer. Furthermore, the carbon in the resultant silicon nitride layer can help trap free hydrogen in the device and prevent boron diffusion exacerbated by free hydrogen. Therefore, due to less free hydrogen and better uniformity, the electrical characteristics of the device are improved.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
  • FIGS. 1A to 1E are cross-sectional views of the fabrication process steps for a gate structure according to one preferred embodiment of this invention.
  • FIGS. 2A to 2F are cross-sectional views of the fabrication process steps for a flash memory according to another preferred embodiment of this invention.
  • DESCRIPTION OF THE EMBODIMENTS
  • Reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts.
  • As mentioned above, as the line-width minimizes and the thickness of each layer shrinks, it is important to enhance the uniformity of certain layers, such as the silicon nitride layer for the offset spacer or the spacer for better-quality device or improved standardization of the devices within the wafer.
  • Currently, it is common to employ SiH4 and NH3 as the reactant gases for forming the silicon nitride layer by the single wafer tools. However, the obtained silicon nitride layer has inferior and unsatisfactory within wafer uniformity, wafer-to-wafer uniformity and lot-to-lot uniformity. Alternatively, furnace can be used to form the silicon nitride layer for the wafers in batch. However, higher thermal budget is required and the production cost is therefore higher.
  • According to this invention, it is proposed to form a carbon-containing silicon nitride layer with better uniformity by employing Si2H6, NH3 and at least one carbon-source precursor as the reactant gases, preferably by single wafer tools but also compatible with furnace processes.
  • According to the present invention, the carbon-containing silicon nitride layer is formed by using disilane (Si2H6), NH3 and at least one carbon-source precursor as the reactant gases, preferably by low pressure CVD (LPCVD). For example, the carbon-source precursor can be selected from the group consisting of TEASAT (triethylarsenate, C6H15AsO4), Trans-LC (C2H2Cl2), TCS (trichlorosilane, SiHCl3), TMAl (trimethyl aluminum, Al(CH3)3), C2H4, C3H6, TEB (triethylborate, B(OC2H5)3), TEPO (triethylphosphate, PO(C2H5O)3), TDMAT (tetrakis-dimethylamino titanium, Ti[N(CH3)2]4) and the combinations thereof. Preferably, the obtained silicon nitride layer contains more than 9% of carbon. By optimizing the process parameters and/or choosing the appropriate carbon-source precursor, the resultant silicon nitride layer can contain up to about 30% of carbon, for example.
  • According to the method proposed in this invention, the carbon-containing silicon nitride layer formed by using disilane (Si2H6), NH3 and at least one carbon-source precursor as the reactant gases by LPCVD is measured to have better within wafer uniformity, wafer-to-wafer uniformity and lot-to-lot uniformity, when compared with the conventional silicon nitride layer. Furthermore, the carbon in the resultant silicon nitride layer can help trap free hydrogen in the device and prevent boron diffusion exacerbated by free hydrogen. Therefore, due to less free hydrogen and better uniformity, the electrical characteristics of the device are improved.
  • The method for forming the carbon-containing silicon nitride layer proposed in this invention is compatible with and can be incorporated in the manufacturing processes of various semiconductor devices. In the following embodiments, the proposed method for forming the carbon-containing silicon nitride layer is incorporated into the fabrication process steps for a gate structure.
  • FIGS. 1A to 1E are cross-sectional views of the fabrication process steps for a gate structure according to one preferred embodiment of this invention. Referring to FIG. 1A, a substrate 100 having a gate dielectric layer 104 and at least an isolation structure 102 is provided. The isolation structure 102 is a shallow trench isolation (STI) structure, for example. A conductive layer 106 is formed on the gate dielectric layer 104. The material of the conductive layer 106 is polysilicon or other suitable materials, for example.
  • As shown in FIG. 1B, a patterned mask layer 120, for example, a patterned resist layer, is formed over the conductive layer 106. Using the patterned mask layer 120 as an etching mask, the conductive layer 106 and the gate dielectric layer 104 are defined to form the gate electrode 105.
  • Then, as shown in FIG. 1C, the patterned mask layer 120 is removed. Later on, a liner layer 108 is formed over the substrate 100. Thereafter, ion implantation is performed to form lightly doped drain (LDD) regions 122 in the substrate 100 at both sides of the gate electrode 105. Then, a passivation layer 112 is conformally formed over the substrate 100 and covering the gate electrode 105. The passivation layer 112 is, for example, a carbon-containing silicon nitride layer.
  • Referring to FIG. 1D, etching back the passivation layer 112 until a top surface of the gate electrode 105 is exposed, so that spacers 112 a are formed on sidewalls of the gate electrode 105.
  • Referring to FIG. 1E, using the spacers 112 a as masks, ion implantation is performed to form source/drain regions 124 in the substrate 100 at both sides of the gate electrode 105 and beside the LDD regions 122.
  • As mentioned above, the uniformity of the passivation layer (silicon nitride layer) 112 is greatly improved by using the method for forming the carbon-containing silicon nitride layer proposed in this invention.
  • Taking silicon nitride passivation layer 112 in the above embodiment as an example, the process parameters of the LPCVD process for forming the carbon-containing silicon nitride layer 112 are as follows. Gas source: disilane (Si2H6) with a gas flow rate less than 50 sccm (standard cubic centimeter per minute), NH3 and the carbon-source precursor (C2H4) with a gas flow rate less than 2 slm (standard liter per minute); the reaction pressure is below 250 Torr and the reaction temperature is below 800° C. The carbon content of the resultant silicon nitride layer ranges from about 9% to about 30%.
  • Using the carbon-containing silicon nitride layer formed by the method proposed in this invention as the spacer, the trapping efficiency of free hydrogen is increased in the device and negative bias temperature instability (NBTI) of the device is improved.
  • FIGS. 2A to 2F are cross-sectional views of the fabrication process steps for a gate structure according to another preferred embodiment of this invention. Referring to FIG. 2A, a substrate 200 having a gate dielectric layer 204 and at least an isolation structure 202 is provided. A conductive layer 206 is formed on the gate dielectric layer 204. The material of the conductive layer 206 can be polysilicon or other suitable materials, for example.
  • As shown in FIG. 2B, a patterned mask layer 220, for example, a patterned resist layer, is formed over the conductive layer 206. Using the patterned mask layer 220 as an etching mask, the conductive layer 206 and the gate dielectric layer 204 are defined to form the gate electrode 205.
  • In FIG. 2C, the patterned mask layer 220 is removed. Later on, a liner layer 208 is formed over the substrate 200 and an offset material layer 210 is conformally formed over the substrate 200 and covering the gate electrode 205. The offset material layer 210 can be a single, carbon-containing silicon nitride layer or a composite layer of a silicon oxide layer and a carbon-containing silicon nitride layer, for example. Either way, the carbon-containing silicon nitride layer is formed by using the method proposed in this invention. The exemplary LPCVD process parameters for forming the carbon-containing silicon nitride layer 210 are: gas source: disilane (Si2H6) with a gas flow rate less than 50 sccm (standard cubic centimeter per minute), NH3 and the carbon-source precursor (C2H4) with a gas flow rate less than 2 slm (standard liter per minute); the reaction pressure is below 250 Torr and the reaction temperature is below 800° C. The carbon content of the resultant silicon nitride layer ranges from about 9% to about 30%.
  • Referring to FIG. 2D, the offset material layer 210 is etched back until a top surface of the gate electrode 205 is exposed, so as to form offset spacers 210 a on both sidewalls of the gate electrode 205. Then, using the offset spacers 210 a as masks, ion implantation is performed to form lightly doped drain (LDD) regions 222 in the substrate 200 at both sides of the gate electrode 205. Afterwards, a passivation layer 212 is conformally formed over the substrate 200 and covering the gate electrode 205. The passivation layer 212 is, for example, a carbon-containing silicon nitride layer or a composite layer comprising at least a carbon-containing silicon nitride layer, for example. The carbon-containing silicon nitride layer is again formed by using the method proposed in this invention, using similar LPCVD process parameters recited in the above step, containing about 9% to about 20% of carbon.
  • Referring to FIG. 2E, etching back the passivation layer 212 until a top surface of the gate electrode 205 is exposed, so that spacers 212 a are formed on the sidewalls of the offset spacers 210 a.
  • Referring to FIG. 2F, using the offset spacers 210 a and the spacers 212 a as masks, ion implantation is performed to form source/drain regions 224 in the substrate 200 and beside the LDD regions 222.
  • According to the preferred embodiments, the above method for forming the carbon-containing silicon nitride layer can be applied to the form the offset spacer and the spacer in the gate structure. However, the above method proposed in this invention can also be applied or incorporated in the fabrication processes of other semiconductor devices.
  • In conclusion, the present invention has at least the following advantages:
  • 1. The present invention provides a method for forming a silicon nitride layer having better within wafer uniformity, wafer-to-wafer uniformity and lot-to-lot uniformity, when compared with the conventional silicon nitride layer.
  • 2. The present invention can increase the carbon content in the resultant silicon nitride layer, thus reducing boron diffusion and improving the electrical characteristics of the device.
  • It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents.

Claims (16)

What is claimed is:
1. A method for forming a gate, comprising:
providing a substrate having a gate dielectric layer thereon;
forming a conductive layer on the gate dielectric layer;
patterning the conductive layer and the gate dielectric layer to form a gate electrode;
forming offset spacers on the sidewalls of the gate electrode, the material of the offset spacers is carbon-containing silicon nitride;
forming a material layer over the substrate and covering the gate electrode, wherein the material layer comprises a carbon-containing silicon nitride layer formed by low pressure chemical vapor deposition (LPCVD); and
etching back the material layer to form spacers over sidewalls of the gate electrode.
2. The method according to claim 1, wherein the carbon-containing silicon nitride layer has a carbon content higher than 9%.
3. The method according to claim 2, wherein the carbon-containing silicon nitride layer has a carbon content ranging from about 9% to about 30%.
4. The method according to claim 1, wherein the carbon-containing silicon nitride layer is formed by a single wafer tool.
5. The method according to claim 1, wherein the carbon-containing silicon nitride layer is formed by using reactant gases including at least a carbon-source precursor, and the carbon-source precursor is selected from the group consisting of TEASAT (triethylarsenate, C6H15AsO4), Trans-LC (C2H2Cl2), TCS (trichlorosilane, SiHCl3), TMAl (trimethyl aluminum, Al(CH3)3), C2H4, C3H6, TEB (triethylborate, B(OC2H5)3), TEPO (triethylphosphate, PO(C2H5O)3), TDMAT (tetrakis-dimethylamino titanium, Ti[N(CH3)2]4) and combinations thereof.
6. The method according to claim 5, wherein a gas flow rate of the carbon-source precursor is less than 2 slm (standard liter per minute).
7. The method according to claim 1, wherein a reaction pressure of the LPCVD for forming the carbon-containing silicon nitride layer is below 250 Torr.
8. The method according to claim 1, wherein a reaction temperature of the LPCVD for forming the carbon-containing silicon nitride layer is below 800° C.
9. The method according to claim 1, the step of forming the offset spacers comprises:
forming a carbon-containing silicon nitride offset material layer over the substrate; and
etching back the carbon-containing silicon nitride offset material layer to form the offset spacers on the sidewalls of the gate electrode.
10. The method according to claim 9, wherein the carbon-containing silicon nitride offset material layer is formed by low pressure chemical vapor deposition (LPCVD) using disilane, ammonia and at least a carbon-source precursor as reactant gases.
11. The method according to claim 10, wherein the carbon-source precursor is selected from the group consisting of TEASAT (triethylarsenate, C6H15AsO4), Trans-LC (C2H2Cl2), TCS (trichlorosilane, SiHCl3), TMAl (trimethyl aluminum, Al(CH3)3), C2H4, C3H6, TEB (triethylborate, B(OC2H5)3), TEPO (triethylphosphate, PO(C2H5O)3), TDMAT (tetrakis-dimethylamino titanium, Ti[N(CH3)2]4) and combinations thereof.
12. The method according to claim 10, wherein a reaction pressure of the LPCVD for forming the carbon-containing silicon nitride offset material layer is below 250 Torr.
13. The method according to claim 10, wherein a reaction temperature of the LPCVD for forming the carbon-containing silicon nitride offset material layer is below 800° C.
14. The method according to claim 9, wherein the carbon-containing silicon nitride offset material layer has a carbon content higher than 9%.
15. The method according to claim 14, wherein the carbon-containing silicon nitride offset material layer has a carbon content ranging from about 9% to about 30%.
16. The method according to claim 9, wherein the carbon-containing silicon nitride offset material layer is formed by a single wafer tool.
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