# Patent

## Title
Nanocrystal non-volatile memory cell and method therefor

## Abstract

A method of forming a semiconductor device includes forming a first dielectric layer over a semiconductor substrate, forming a plurality of discrete storage elements over the first dielectric layer, thermally oxidizing the plurality of discrete storage elements to form a second dielectrics over the plurality of discrete storage elements, and forming a gate electrode over the second dielectric layer, wherein a significant portion of the gate electrode is between pairs of the plurality of discrete storage elements. In one embodiment, portions of the gate electrode is in the spaces between the discrete storage elements and extends to more than half of the depth of the spaces.

## Background
RELATED APPLICATIONS
This application is related to U.S. patent application having docket number MT10188TP, titled “Nanocrystal Non-Volatile Memory Cell and Method Therefor,” assigned to the assignee hereof and filed even date herewith
FIELD OF THE INVENTION
The invention relates to integrated circuits and, more particularly, to integrated circuit memories that have memory cells with nanocrystals.
BACKGROUND OF THE INVENTION
The use of nanocrystals in non-volatile memories (NVMs) was primarily to have redundancy in each memory cell so that if there were a weak spot in a dielectric layer around the storage layer causing leakage of charge, then only a single nanocrystal in the storage layer would be adversely impacted and the remaining nanocrystals would still retain charge. There are typically difficulties with limited memory window, threshold voltage shift during program/erase cycling endurance, and read disturb of bits in a programmed state that are greater for nanocrystal NVM cells than for floating gate memory cells. The limited memory window arises from coulomb blockade effects that limit the charge storage capacity of the nanocrystals so that the total charge stored is less resulting in less threshold voltage differential between the logic high and logic low states. The program/erase cycling results in charge trapping, which can be cumulative, in the dielectric above the nanocrystals and thus reducing endurance. In the case of the floating gate, the charge is prevented from reaching the dielectric overlying the floating gate by the floating gate itself. Read disturb in bits that are in a programmed state arises due to the relatively higher field above the nanocrystals compared to the electric field above the floating gate in a floating gate device.
Thus, there is a need for NVM memory cells having nanocrystals overcoming or at least reducing these difficulties.



BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and further and more specific objects and advantages of the invention will become readily apparent to those skilled in the art from the following detailed description of a preferred embodiment thereof taken in conjunction with the following drawings:
FIG. 1 is a cross section of a semiconductor device structure at a stage in processing according to a first embodiment of the invention;
FIG. 2 is a cross section of the semiconductor device structure of FIG. 1 at a subsequent stage in processing to that shown in FIG. 1;
FIG. 3 is a cross section of the semiconductor device structure of FIG. 2 at a subsequent stage in processing to that shown in FIG. 2;
FIG. 4 is a cross section of the semiconductor device structure of FIG. 3 at a subsequent stage in processing to that shown in FIG. 3;
FIG. 5 is a cross section of the semiconductor device structure of FIG. 4 at a subsequent stage in processing to that shown in FIG. 4;
FIG. 6 is a cross section of a semiconductor device structure at a stage in processing according to a second embodiment of the invention;
FIG. 7 is a cross section of the semiconductor device structure of FIG. 6 at a subsequent stage in processing to that shown in FIG. 6;
FIG. 8 is a cross section of the semiconductor device structure of FIG. 7 at a subsequent stage in processing to that shown in FIG. 7;
FIG. 9 is a cross section of the semiconductor device structure of FIG. 8 at a subsequent stage in processing to that shown in FIG. 8; and
FIG. 10 is a cross section of the semiconductor device structure of FIG. 9 at a subsequent stage in processing to that shown in FIG. 9;



DETAILED DESCRIPTION OF THE INVENTION
In one aspect a memory device has nanocrystals that are substantially all much larger than nanocrystals typically used in memory cells. The oversized nanocrystals establish a contour that the overlying dielectric follows on its surface. The result is that the subsequent overlying gate has this contour as well because the gate wraps around the nanocrystals to some extent. This has the effect of providing better capacitive coupling between the gate and the nanocrystals which results in lower electric field in the dielectric overlying the nanocrystals. The reduced electric field has the effect of improving endurance, memory window, and read disturb. This is better understood by reference to the drawings and the following description.
Shown in FIG. 1 is a semiconductor device structure 10 comprising a semiconductor layer 12, a gate dielectric layer 14 on semiconductor layer 12, and a plurality of nanocrystals 16 on gate dielectric 14. Nanocrystal 18 is one of plurality 16 and is exemplary of nanocrystals 16. Semiconductor layer 12 may be part of a semiconductor-on-insulator (SOI) or bulk substrate. Semiconductor layer 12 is preferably silicon but could be another semiconductor material. Gate dielectric 14 is preferably thermally grown silicon oxide but could be another gate dielectric material. Nanocrystals 16, which function as storage elements, are preferably about 25 nanometers in diameter which is about 5 times more than is typically used for NVM memories using nanocrystals. They can be lower or higher diameter though but should be at least 12 nanometers in diameter. Nanocrystals 16 are preferably made using a CVD process using a silicon based precursor but another process may also be effective.
CVD silicon-based processes are known to be able to achieve the relatively large diameters. One such process uses silane as the precursor at a temperature range of 500-550 degrees Celsius at a partial pressure 700-800 millitorr for about 500 seconds. Additionally, nitrogen is co-flowed with the silane to obtain a total pressure of about 18 torr. Another process uses disilane as the precursor at a temperature range of 450-500 degrees Celsius, at a partial pressure at 80-100 millitorr, for about 300 seconds. Similar for this process, nitrogen is co-flowed with the disilane to obtain a total pressure of about 18 torr. In both processes, an anneal at 750 degrees Celsius in nitrogen is performed for 10 seconds. These processes do result in some variation, even more than two to one in some cases, in diameter across a wafer. What can occur is that two growing nanocrystals can come in contact and coalesce into a larger size nanocrystal. For the example shown, none of the nanocrystals exhibit this coalescing of two nanocrystals. Yet another silicon-precursor process that is more complex but that provides good uniformity and controllable spacing is described in U.S. patent application Ser. No. 11/065,579 and is incorporated herein by reference.
Shown in FIG. 2 is semiconductor device structure 10 after formation of a nitrided oxide layer 20 around plurality 16 of nanocrystals. This is achieved using a thermal oxide process similar to that used for forming gate dielectrics that are very thin, such as 20 Angstroms or less.
Shown in FIG. 3 is semiconductor device structure 10 after forming control dielectric 22 of high temperature oxide (HTO). HTO is typical for the oxide over the nanocrystals. The thickness of the HTO around nanocrystals 16 is preferably no more than 80 percent of the diameter of nanocrystals 16. For the case that nanocrystals 16 are chosen to be 250 Angstroms in diameter, the preferred thickness of control dielectric 22 is 80 Angstroms. In such case, the thickness is only about 32 percent of the diameter of nanocrystals 16. Nanocrystals 16 are preferably spaced apart by a distance greater than the thickness of control dielectric 22 but less than twice the thickness of control dielectric 22. In this example, the spacing that fits half way between these two requirements is about 120 Angstroms. As shown, control dielectric 22 has a top surface that follows the contour of the round top portions of nanocrystals 16.
Shown in FIG. 4 is semiconductor device structure 10 after depositing a gate material 24 over control dielectric 22. Gate material 24 is preferably polysilicon but could another material such as one of the metals being considered for use as a gate for MOS transistors. The effect is that gate material 24 is in proximity to the top surface of nanocrystals 16 according to the top surface of control dielectric 22 which in turn follows the contour of the top portions of nanocrystals 16.
Shown in FIG. 5 is semiconductor device structure 10 after performing conventional process steps for forming a transistor memory cell after the gate material has been deposited over the nanocrystals. In FIG. 5, semiconductor device structure 10 shows an etched gate material 24 to form a gate, a sidewall spacer 26 around the gate, remaining nanocrystals 16 that are under the gate, and source/drains 28 and 30 on opposite sides of the gate and in semiconductor layer 12.
The resulting memory cell shown in FIG. 5 provides better coupling between the gate and nanocrystals 16 due to the top surface of control dielectric 22 following the contour of the top portions of nanocrystals 16. With improved coupling between the gate and nanocrystals 16 there is less voltage drop between the gate and nanocrystals 16 for a given gate voltage. This results in lower electrical field in the control dielectric 22 during operation of the device. The reduced electric field mitigates electron tunneling from the gate into nanocrystals during erase and electron tunneling from nanocrystals to gate during programming or READ. As a result improved memory window is obtained through better erase and programming, reduced read disturb, and improved endurance. Further, the lower electric field also results in less acceleration of electrons injected during programming but not captured by nanocrystals. The reduced acceleration of these electrons in the control dielectric reduces charge trapping in the control dielectric and improves program-erase cycling endurance of the memory device.
Shown in FIG. 6 is a semiconductor device structure 50 comprising a semiconductor substrate 52, a gate dielectric layer 54 on semiconductor substrate 52, and a nitrided layer 56 formed at the surface of gate dielectric layer 54, and a plurality of nanocrystals 58 formed on nitrided layer 56. Nanocrystal 60 is one of plurality 58 and is exemplary of nanocrystals 58. Semiconductor layer 52 may be part of a semiconductor-on-insulator (SOI) or bulk substrate. Semiconductor layer 52 is preferably silicon but could be another semiconductor material. Gate dielectric 54 is preferably thermally grown silicon oxide but could be another gate dielectric material. Nanocrystals 58 are preferably hemispherically shaped and about 25 nanometers in diameter which is about 5 times more than is typically used for NVM memories using nanocrystals. They can be lower or higher diameter though but should be at least 12 nanometers in diameter. Nanocrystals 58 are made in substantially the same way as nanocrystals 16 of FIGS. 1-5, but are hemispherical due to being formed on nitrided layer 56 instead of on an oxide layer such as gate dielectric layer 14 of FIGS. 1-5. In this case nanocrystals 58 are spaced further apart, preferably about 25 nanometers apart. This is achieved in the described silane and disilane processes by increasing the temperature of deposition. For example, in the silane process, the temperature is increased to 600 to 650 Celsius. For the disilane process, the temperature is increased to 550 to 600 degrees Celsius. Nitrided layer 56 is formed by exposing gate dielectric layer 54 to decoupled plasma nitridation. Nitrided layer 56 is preferably about 10 Angstroms in thickness. Gate dielectric layer 54 has a thickness of preferably about 50 Angstroms.
Shown in FIG. 7 is semiconductor device structure 50 after thermally growing a nitrided oxide layer 62 of about 5 to 10 nanometers in thickness. One way this can be achieved is by exposing nanocrystals 58 to nitric oxide (NO) at a relatively high temperature such as about 850 degrees Celsius.
Shown in FIG. 8 is semiconductor device structure 50 after deposition of a control dielectric layer 64 on nitrided oxide layers of nanocrystals 58 and on nitrided layer 56 that is exposed in spaces between the various nanocrystals 58. This may be an optional layer because nitrided oxide layers 62 provide a dielectric that functions as a control dielectric for nanocrystals 58.
Shown in FIG. 9 is semiconductor device structure 50 after depositing a layer of gate material 66 over nanocrystals 58. Gate material is preferably polysilicon but could be another material such as a metal being considered as a gate for MOS transistors.
Shown in FIG. 10 is semiconductor device structure 50 after performing conventional process steps for forming a transistor memory cell after the gate material has been deposited over the nanocrystals similar as for semiconductor device 10 of FIG. 5. In FIG. 10, semiconductor device structure 50 shows an etched gate material 66 to form a gate, a sidewall spacer 68 around the gate, remaining nanocrystals 58 that are under the gate, and source/drains 70 and 72 on opposite sides of the gate and in semiconductor layer 52. The result is that there is a substantial portion of the gate between pairs of nanocrystals 58, pairs being ones that are adjacent.
The resulting memory cell shown in FIG. 10, similar to that shown in FIG. 5, provides better capacitive coupling than is typical for nanocrystal NVMs between the gate and nanocrystals 58 due to the top surface of control dielectric 22 following the whole contour of the portion of the nanocrystals 16 above nitrided layer 56. The gate has a substantial portion that is between adjacent nanocrystals. With improved capacitive coupling between the gate and nanocrystals 16 there is less voltage drop between the gate and nanocrystals 16 for a given gate voltage. The result of this reduced voltage drop is improved memory window through better erase and better programming, reduced read disturb, and improved program-erase cycling endurance.
In this example, the control dielectric layer 64 is optional if the nitrided oxide layer 62 on nanocrystals 58 is sufficient to withstand the voltage applied to the gate for programming and erase for nanocrystals 58 and also that gate dielectric 54 and nitrided layer 56 are sufficient to withstand the voltage applied to the gate for programming and erase. As a further alternative, nitrided layer 56 may be omitted. In such case, the exposed spaces between nanocrystals 58 will grow some nitrided oxide during the application of the nitric oxide that causes the growth of nitrided oxide layer 62 on nanocrystals 58. This would have the effect of reducing the need for adding control dielectric 64. In such case nanocrystals would be spherical because they would have been formed on an oxide layer. This is somewhat disadvantageous because a portion of the gate would be below the center point of the sphere and thus cause a partial bias against the desired direction of electron movement during program and erase. The adverse bias would be small and may be worth the benefit of the increase in gate dielectric thickness.
Various other changes and modifications to the embodiments herein chosen for purposes of illustration will readily occur to those skilled in the art. For example, nanocrystals were described as being the storage elements for the memory cells but a possible alternative for the storage elements could be nanowires. To the extent that such modifications and variations do not depart from the spirit of the invention, they are intended to be included within the scope thereof which is assessed only by a fair interpretation of the following claims.

## Claims

1. A method of forming a semiconductor device, the method comprising:
forming a first dielectric layer over a semiconductor substrate;
forming a plurality of discrete storage elements over the first dielectric layer;
thermally oxidizing the plurality of discrete storage elements to form a second dielectric layer over the plurality of discrete storage elements; and
forming a gate electrode over the second dielectric layer, wherein a portion of the gate electrode extends below a height of the plurality of discrete storage elements is thereby between adjacent pairs of the plurality of discrete storage elements.

2. The method of claim 1, wherein thermally oxidizing the plurality of discrete storage elements to form the second dielectric layer further comprises increasing a thickness of the first dielectric layer.

3. The method of claim 1, further comprising:
forming a layer comprising nitride over the first dielectric layer prior to forming the plurality of discrete storage elements, wherein forming the plurality of discrete storage elements further comprise forming the plurality of discrete storage elements over the layer comprising nitride; and
forming a third dielectric layer over the second dielectric layer.

4. The method of claim 3, wherein forming the plurality of discrete storage elements comprises forming the plurality of discrete storage elements, wherein the discrete storage elements are hemispherical.

5. The method of claim 3, wherein forming the plurality of discrete storage elements comprises forming the plurality of discrete storage elements, wherein the discrete storage elements are spherical.

6. The method of claim 3, wherein:
forming the first dielectric layer comprises forming a tunnel dielectric; and
thermally oxidizing to from the second dielectric layer comprises forming a nitrided oxide layer on each of the plurality of discrete storage elements.

7. The method of claim 3, wherein:
forming the third dielectric layer is further characterized by the third dielectric layer being part of a control dielectric.

8. The method of claim 7, wherein forming the third dielectric layer is further characterized by the third dielectric having a tor surface with a contour that follows the plurality of discrete storage elements.

9. A method of forming a semiconductor device, the method comprising:
forming a first discrete storage element and a second discrete storage element over a semiconductor substrate, wherein:
the first discrete storage element and the second discrete storage element are separated by a space; and
the space has a depth; and

forming a first portion of a gate electrode within the space and over the first and second discrete storage elements, wherein the first portion extends within the space more than half of the depth.

10. The method of claim 9, further comprising:
forming a first dielectric layer over the semiconductor substrate, wherein the first discrete storage element and the second discrete storage element are formed over the first dielectric layer; and
thermally oxidizing the first and second discrete storage elements to form a second dielectric layer of nitrided oxide over the first and second discrete storage elements.

11. The method of claim 10, wherein the step of thermally oxidizing the first and second discrete storage elements to form the second dielectric layer further comprises increasing a thickness of the first dielectric layer.

12. The method of claim 10, further comprising:
forming a nitrided layer over the first dielectric layer prior to forming the first and second discrete storage elements, wherein forming the first and second discrete storage elements further comprises forming the plurality of discrete storage elements over the nitrided layer; and
forming a third dielectric layer over the second dielectric layer.

13. The method of claim 9, wherein forming a first portion of the gate electrode further comprises forming the first portion of the gate electrode, wherein the first portion fills the space.