Method of forming an isolation layer and method of manufacturing a trench capacitor

Abstract

A two-step etch process is used to form a vertical collar oxide within the upper portion of a trench capacitor. The first step uses CF4/SiF4/O2 chemistry and ends when the bottom of the collar within the trench is opened although a thin oxide layer still remains on the surface of the PAD-nitride. The second etch step uses C4F8 chemistry to completely remove the remaining silicon oxide layer. The process provides a good uniformity in thickness of the PAD-nitride layer and sufficient collar oxide thickness in the very top section of the collar oxide. The process is applicable for manufacturing deep trench capacitors for DRAM devices.

Description

[0001] The invention refers to a method of forming an isolation layer on the sidewalls of a trench whereby a semiconductior wafer that comprises a substrate is provided, the substrate having a first isolation layer arranged on a main surface of the substrate and having a trench arranged within the substrate. A second isolation layer is being deposited on the wafer, the horizontal portions of the second isolation layer are to be etched. The invention further refers to a method of manufacturing a trench capacitor that uses the above method of forming an isolation layer on the sidewalls of the trench.

[0002] In the field ofmanufacturing dynamic random access memories (DRAMs) the storage capacitor is formed as a deep trench capacitor within the semiconductor substrate. The lower portion of the trench comprises the storage node having one plate of the capacitor within the substrate, having the dielectric layer arranged on the sidewalls of the lower portion of the trench and having the second electrode arranged preferably as a polysilicon filling material within the trench. The upper portion of the trench is isolated from the substrate by a so-called collar isolation, preferably a thick silicon oxide collar layer. In the sequence of precess steps for the manufacturing of the trench capacitor, the semiconductor wafer is provided with the storage node already completed. At this point, the lower portion of the trench has the dielectric layer arranged on its sidewalls and is filled with polysilicon. On the surface of the wafer, a PAD-silicon nitride layer is already deposited. The upper portion of the deep trench is still open and subject to further processing. Now, a conformal isolation layer, preferably a silicon oxide layer, is deposited on the wafer. As a result, the conformal layer of silicon oxide is present on the sidewalls of the upper portion of the trench, on the bottom surface of said upper portion of the trench, and on the silicon nitride layer on the main surface of the semiconductor wafer. Within the upper portion of the trench, the silicon oxide layer is directly deposited onto the upper end of the polysilicon filling material which is arranged in the lower portion of the deep trench. At this stage, the process of manfacturing the trench capacitor continues with the removal of the horizontal portions of the conformal silicon oxide layer, e. g. the portions being arranged on the bottom of the upper portion of the deep trench. As a result, the vertical portions of the silicon oxide layer remain on the sidewalls of the upper portion of the deep trench as a collar isolation in order to electrically isolate the further filling of the upper portion of the deep trench from the surrounding substrate of teh semiconductor wafer. The bottom of the upper portion consisting of e. g. silicon oxide is opened to ensure the electrical accessibility of the polysilicon in the lower portion of the trench. At a later phase of the manufacturing process of a DRAM device, an active area comprising an access transistor is formed within the substrate adjacent to the collar isolation.

[0003] The opening of the bottom surface of the trench must be performed without damaging the silicon nitride layer. For such removal of silicon oxide, a dry etch process using the etch gas C4F8 is already known. The etching with C4F8 provides sufficient selectivity between silicon oxide and silicon nitride on the surface of the wafer and moreover provides a good etch stop performance on the bottom of the trench versus the polysilicon filling material. A disadvantage of the etch gas C4F8, however, is that the very top section of the vertical part of the collar oxide is also etched to a larger extend due to the high silicon oxide etch rate of C4F8. This is particular true when used in capacitively working plasma etch chambers, where a high sheath voltage causes a high ion energy acceleration to the wafer surface which results in a high oxide etch rate. As a consequence said very top vertical section of the collar oxide may be recessed to such an extend that the silicon oxid (PAD-oxide) hidden behind the collar oxide underneath the PAD-nitride subsequent process steps. One of the subsequent process steps is an isotropic silicon wet etch which can undercut the PAD-silicon nitride layer. The reliability of the process is less stable and the production yield for DRAM devices is lower.

[0004] It is an object of the invention to provide a more stable and more reliable process of forming an isolation layer on the sidewalls of a trench, and it is a further object of the invention to provide a more stable and more reliable method of manufacturing a trench capacitor having such an isolation layer.

[0005] According to the invention, the object with respect to the method of forming an isolation layer is achieved by a method of forming an isolation layer on the sidewalls of a trench comprising the steps of: providing a semiconductor wafer comprising a substrate having a first isolation layer stack arranged on a main surface of the substrate and having a trench arranged in the substrate; depositing a second isolation layer on the wafer; etching the wafer in a first step with a first etch gas composition comprising the gases CF4 and SiF4 and O2; etching the wafer in a second etch step subsequent to said first etch step with a second etch gas composition comprising the gas C4F8.

[0006] With respect to the method of manufacturing a trench capacitor, the object is achieved by a method of manufacturing a trench capacitor using the aforementioned method, wherein the semiconductor wafer further comprises a deep trench having a lower portion with a dielectric layer arranged on its sidewalls and being filled with silicon and having an upper portion being arranged above the lower portion with said second isolation layer being deposited on the sidewalls of said upper portion of said deep trench, and on the surface of said silicon arranged within the lower portion of said deep trench, and on the surface of said first isolation layer stack.

[0007] The methods according to the invention benefit from a two-step etch process for the removal of the horizontal portions of the second isolation layer so that only the vertical portions remain, thereby forming a reliable collar oxide within the trench capacitor. The two steps of the etch process have different properties that are adopted to the progressing of the overall etch procedure. In this respect, the first etch step comprises a gas composition of CF4, SiF4 and O2. This etch gas composition is known to etch silicon oxide, silicon nitride, and polysilicon at substantially the same rate, e.g. without substantial selectivity to each other. The etch rate of silicon oxide on the top of the wafer can be adjusted to be rather low. There is only little removal of silicon oxide on the top surface of the wafer so that it can be assured that there is always a sufficiently thick silicon oxide layer on the silicon nitride layer that protects the silicon nitride. At the bottom of the trench, the etch rate of silicon oxide is rather reasonable so that the silicon oxide is fully removed from the underlying polysilicon filling material. As a result of the first etch step using CF4, SiF4, and O2, the silicon oxide on the bottom of the trench is removed whereas a thin silicon oxide layer is still present on the top main surface of the wafer protecting the silicon nitride. Moreover, the very top section of the vertical collar oxide is not damaged. The different etch rates for silicon oxide on the bottom of the trench and on the top surface are due to the fact that there is etching and deposition of silicon oxide on the top surface and the trench bottom at the same time. At the trench bottom, the removal of silicon oxide dominates strongly over the deposition of silicon oxide, whereas at the top surface the removal dominates only slightly over the deposition resulting in a higher overall oxide etch rate at the trench bottom than at the top surface.

[0008] In the second etch step, the etch chemistry C4F8 which is preferably diluted with CO or alternatively CO and O2. This chemistry is known for substantially high selectivity between silicon oxide and silicon nitride so that the thin layer of silicon oxide that was left at the end of the first etch step can be etched away in a rather uniform way without damaging the underlying silicon nitride layer. It is to be noted that the vertical portion of the silicon oxide layer at the very top of the collar is recessed during the second etch step, due to the aggressiveness of the etch gas with respect to silicon oxide. The amount of recess, however, can be tolerated and is clearly within the thickness of the silicon nitride layer and does definitely not reach below the silicon nitride layer. The silicon substrate that is to be protected by the collar oxide is, therefore, sufficiently covered at the very top portion of the trench where the silicon substrate contacts the silicon nitride layer so that there is no undercut by subsequent application of wet etch chemicals.

[0009] As an overall consequence, the collar etch combines the advantages of C4F8 and CF4/SiF4/O2 etch properties for the etching of the collar oxide for the manufacturing of a trench capacitor. As a result, a defined nitride surface is provided on the top of the wafer having good uniformity of the nitride layer, the collar oxide is only recessed little at the trench top and the collar oxide at the trench bottom is opened perfectly.

[0010] The first etch step using CF4/SiF4/O2 chemistry is finished when the silicon oxide is completely removed from the bottom of the trench. The second etch step using C4F8 chemistry is finished when the silicon oxide on top of the wafer, i. e. on top of the silicon nitride, is completely removed. The first etch step is run by time or endpoint while the second etch step is finished by endpoint. The second etch step employs a polymerizing chemistry. It is therefore advantageous tointroduce a subsequent sputter etch with O2 to remove probable polymer residues which is preferably followed by a wet etch clean.

[0011] As already stated, the isolation layer on the vertical sidewalls of the trench are particularly useful for a collar isolation oxide layer which isolates the upper part of a trench capacitor. The upper portion of the overall deep trench capacitor which is subject to the aforementioned etch processes serves to isolate the subsequent polysilicon filling og the trench from the surrounding silicon substrate where the active areas including access transistors are subsequently formed. The lower portion of the trench capacitor serves as the storage node comprising the two electrodes of the capacitor.

[0012] The invention will now be described in detail with refernce to the various figures within the drawings.

[0013] FIG. 1 shows a cross-section of a deep trench capacitor after the deposition of a silicon oxide layer.

[0014] FIG. 2 shows a cross-section of the upper part of the deep trench capacitor after the first etch step using CF4/SiF4/O2 and etch chemistry.

[0015] FIG. 3 shows the same cross-section at the end of the process after the second etch step using C4F8 etch chemistry.

[0016] FIG. 4 shows a comparable cross-section after a conventional etch using C4F8 etch chemistry only.

[0017] The cross-section depicted in FIG. 1 shows a semiconductor wafer 10 having a silicon substrate 11. Within the substrate, a deep trench is formed having a lower portion 12 and an upper portion 13. The lower portion 12 serves as the storage node of a capacitor arranged within the deep trench. The storage node comprises a first capacitor electrode 15 arranged within the substrate, a dielectric layer 14 covering the sidewalls of the lower portion 12 of the deep trench and a second electrode 16 arranged within the trench. The inner electrode 16 is comprised of polysilicon. The polysilicon filling 16 as well as the dielectric layer 14 end within the lower portion 12 of the deep trench. The upper portion 13 of the deep trench is now subject to the subsequent process steps.

[0018] The semiconductor wafer has a PAD-silicon nitride layer 18 on its top surface. The PAD nitride 18 remains during various process steps on the layer and must, therefore, not be damaged by the etching steps. A conformal oxide layer 17 is deposited on the wafer surface and conformally covers the top surface 172, the vertical sidewalls 174 of the upper portion 13 of the trench and the horizontal bottom 171 of the trench forming a contact area to the polysilicon fill material of the lower portion 12 of the trench. The thickness of the deposited layer 17 can be different on various areas of the wafer, e. g. the layer may be slightly thicker on the edge of the wafer compared to the center of the wafer. The goal is to remove all horizontal portions 172, 171 of the silicon oxide so that only the vertical portions 174 remain within the upper portion 13 of the trench covering the vertical sidewalls of the portion 13 of the trench. The collar isolation 174 serves to isolate the subsequently introduced polysilicon filling of the upper portion 13 of the trench from the surronding bulk silicon 11. Adjacent to the collar oxide, e. g. in the area 111 of the silicon substrate, a horizontal or a vertical access transistor is to be formed. The deep trench capacitor and the access transistor together are considered a storage cell in a dynamic random access memory (DRAM).

[0019] In a first etch step according to the invention, the result of which is shown in FIG. 2, the horizontal surface 172 is partially etched and th ehorizontal surface 171 of the silicon oxide layer 17 is fully removed, whereas the vertical portions 174 are still present. The first etch step uses an etch gas composition with the chemicals CF4, O2, SiF4 (carbon tetra fluoride, oxygen, silicon tetra fluoride). The etching is performed in a high-density plasma reactor. The etching opens the bottom of the trench and fully removes the previously present portion 171 of the silicon oxide layer and etches slightly into the polysilicon filling of the lower portion of the trench leaving a bow-shaped surface. On the top surface, the silicon oxide layer is only partially removed so that the underlying silicon nitride layer 18 is still completely covered by silicon oxide 172. Since the etch rate of polysilicon is about three times higher than the etch rate of silicon oxide, the etch chemistry readily attacks the polysilicon fill 16 within the trench and provides a good end point signal. In contrast, the etch process diminishes the oxide thickness on the top portion 172 on the wafer only slightly due to a combined etch/deposition reaction so that oveall a good opened collar is provided on the bottom of the trench. It is to be remarked that at the very top section 173 of the collar oxide in the area where the collar oxide contacts the nitride layer 18, the oxide layer is still present. The removal of the silicon oxide portions 171, 172 may be varying from the center to the edge of the wafer. In any case, there is sufficient thickness of oxide 172 on top of the wafer so that the silicon nitride layer 18 is not attacked during the first step.

[0020] After the situation shown in FIG. 2 has been reached by a fixed etch time or appropriate endpointing, the second etch step is started using different etch chemistries. The resulting structure is shown in FIG. 3. The etch gas composition during the second etch step uses C4F8, CO, and O2 (cyclo butane octa fluoride, carbon monoxide, oxygen). This etch chemistry etches silicon oxide with reasonable selectivity to silicon nitride. The thin silicon oxide layer 172 remaining at the end of the first etch step shown in FIG. 2 will now be fully removed from the silicon nitride layer 18. Due to the good selectivity between silicon oxide and silicon nitride almost no nitride is lost and the good nitride uniformity achieved during the nitride deposition is retained. Due to the relatively high etch rate of silicon oxide, the top section 173 of the vertical collar oxide is attacked at the same time. The process time required for the second etch step, however, is established such that, although the top section 173 being recessed, the removal of vertical collar oxide in the region 173 ends within the silicon nitride layer 18 so that the PAD-oxide 19 underneath the PAD-nitride layer 18 is well enough protected by a sufficiently thick vertical collar oxide so that subsequent process steps, especially wet etch steps, do not attack the silicon oxide 19 and under cut of the silicon nitride 18 is avoided.

[0021] As shown in FIG. 4, a prior art etch process which only uses C4 F8 chemistry damages the vertical portion of the collar oxide on the uppermost section of the trench heavily so that the protection of the silicon oxide 19 underneath the PAD-silicon nitride 18 in this area by the collar oxide is not sufficient to avoid any further attack by a subsequent wet etch step. In the cross-section shown in FIG. 4, an undercut of silicon nitride would occur at location 191, which is the portion of the PAD-oxide 19 adjacent to the trench.

[0022] When compared to a conventional method shown in FIG. 4, the two-step etch process, the result of which is shown in FIG. 3, has substantially more collar oxide thickness left to protect the portion 191 of the PAD-silicon oxide 19. Although the thickness of silicon oxide on the top surface is varying across the wafer after the first etch step e. g. being thicker in the wafer center compared to the wafer etch, the high etch rate of the employed C4F8 chemistry for silicon oxide compared to the low etch rate of silicon nitride enables to stop the second etch step with substantially all silicon oxide being removed from the silicon nitride without reducing the thickness of the silicon nitride layer.

[0023] The surface of the silicon nitride layer 18 shown in FIG. 2 has a good uniformity in thickness. However, it may happen that polymer residues are still present. In this case, the wafer surface on the top of the wafer, the trench sidewalls and especially the trench bottom must be cleaned with an additional O2-sputter etch which is preferably followed by wet clean. In particular, the surface 161 of the inner electrode 16 and the top surface of the PAD-nitride 18 are cleaned from the polymer residues from the second etch step.

[0024] Finally, all horizontal layer portions of the previously deposited silicon oxide layer 17 are removed and only the vertical portions 174 of the silicon oxide layer remain after the above described two-step etch process forming a collar isolation that isolates the subsequently to be formed inner filling of the upper portion 13 of the trench from the surrounding silicon substrate 11 that will further contain active areas with access transistors. The inner portion of the trench will be further filled with doped polysilicon in order to provide a conducting inner electrode of the trench capacitor. The subsequent polysilicon fill (not shown in the figure) will then be contacted to the active area in the semiconductor substrate, e. g. by a buried strap.

[0025] The invention is referably applicable to smaller device structures, e. g. down to and less than 110 nm (nanometers). The process performance and the reliability of the manufactured products is increased. The process can be implemented on various plasma etching tools, e. g. RIE- or high-density plasma etchers.

[0026] Attached are various examples for process parameters for etching 300 mm-wafers in a process according to the invention.

[0027] Example for the first etch step:

Total gas flow:      150-400 sccm
Gases:               C4F8, Ar (optional CO and/or O2)
Molar fraction C4F8: 0.01-0.10

[0028] 3. Example:

Tool:                300 mm dual frequency plasma etcher
Power top:           500-1500 W
Power bottom:        0-500 W
Pressure:            100-400 mTorr
Total gas flow:      500-1000 sccm
Gases:               C4F8, Ar (optional CO and/or O2)
Molar fraction C4F8: 0.01-0.10

[0029] 4. Example:

Tool:                300 mm magnetically enhanced reacitve
                     ion plasma etcher
Power:               1000-2500 W
Magnetic field:      0-20 G
Pressure:            50-150 m Torr
Total gas flow:      200-500 sccm
Gases:               C4F8, Ar (optional CO and/or O2)
Molar fraction C4F8: 0.01-0.10

[0030]

List of reference numerals
10       semiconductor wafer
11       substrate
111      active area
112, 113 portions of substrate
12       lower portion of trench
13       upper portion of trench
14       dielectric
15, 16   capacitor electrodes
17       silicon oxide layer
171      silicon oxide layer at trench bottom
172      silicon oxide layer at wafer surface
173      silicon oxide layer at upper edge
174      silicon oxide layer at collar
18       silicon nitride layer, PAD-nitride
19       silicon oxide layer, PAD-oxide
161      surface of capacitor electrode
191      silicon oxide layer adjacent to trench

Claims

1. A method of forming an isolation layer on the sidewalls of a trench, comprising: a semiconductor wafer comprising a substrate having a first isolation layer stack arranged on a main surface of the substrate and having a trench arranged in the substrate; depositing a second isolation layer on the wafer etching the wafer with a first etch gas composition comprising the gases CF4 and SiF4 and 02; and etching the wafer in a second etch step subsequent to the first etch step with a second etch gas composition comprising the gas C4F8.

2. The method according to claim 1, wherein the second etch gas compositions further comprises at least one of the gases CO and 02.

3. The method according to claim 1, wherein the first etch step is stopped when a portion of the second isolation layer, which is arranged on the bottom of the trench, is removed.

4. The method according to claim 3, wherein the first etch step is stopped when a portion of the second isolation layer, which is arranged on the first isolation layer stack completely covers the first isolation layer stack.

5. The method according to claim 1, the first isolation layer stack comprises silicon nitride and the second isolation layer comprises silicon oxide.

6. The method according to claim 1, further comprising sputter etching using 02 to clean the surface of a capacitor electrode arranged within the trench and the surface of the first isolation layer stack from residues of the second etch step.

7. A method of manufacturing a trench capacitor, comprising: a method of forming an isolation layer on the sidewalls of a trench, providing a semiconductor wafer comprising a substrate having a first isolation layer stack arranged on a main surface of the substrate and having a trench arranged in the substrate; depositing a second isolation layer on the wafer etching the wafer with a first etch gas composition comprising the gases CF4 and SiF4 and 02; and etching the wafer in a second etch step subsequent to the first etch step with a second etch gas composition comprising the gas C4F8; wherein the semiconductor wafer further comprises a deep trench having a lower portion with a dielectric layer arranged on its sidewalls, the deep trench being filled with silicon, the deep trench having an upper protion being arranged above the lower portion, the second isolation layer being deposited onthe sidewalls of the upper portion of th edeep trench, on the surface of the silicon arranged within the lower portion of the deep trench, and on the surface of the first isolation layer stack.

8. The method according to claim 7, wherein the second isolation layer is a collar isolation and the upper portion of the deep trench is further filled with doped silicon.

9. The method according to claim 6, wherein the sputter etching is subsequent to the second etch step.

10. The method according to claim 7, wherein the second etch gas compositions further comprises at least one of the gases CO and O2.

11. The method according to claim 7, wherein the first etch step is stopped when a portion of the second isolation layer, which is arranged on the bottom of the trench, is removed.

12. The method according to claim 11, wherein the first step is stopped when a portion of the second isolation layer, which is arranged on the first isolation layer stack completely covers the first isolation layer stack.

13. The method according to claim 7, the first isolation layer stack comprises silicon nitride and the second isolation layer comprises silicon oxide.

14. The method according to claim 7, further comprising a sputter etching using 02 to clean the surface of a capacitor electrode arranged within the trench and the surface of the first isolation layer stack from residues of the second etch step.

15. The method according to claim 14, wherein the sputter etching is subsequent to the second etch step.