Memory devices including gettering agents in memory charge storage structures
10734491 ยท 2020-08-04
Assignee
Inventors
Cpc classification
H01L29/42324
ELECTRICITY
H01L29/66833
ELECTRICITY
H01L29/511
ELECTRICITY
G11C14/0018
PHYSICS
H01L29/40114
ELECTRICITY
H01L29/42332
ELECTRICITY
H01L29/7881
ELECTRICITY
H01L29/4916
ELECTRICITY
H01L21/44
ELECTRICITY
G11C16/0483
PHYSICS
International classification
H01L29/423
ELECTRICITY
H01L21/28
ELECTRICITY
H01L21/44
ELECTRICITY
G11C14/00
PHYSICS
H01L29/49
ELECTRICITY
H01L29/66
ELECTRICITY
Abstract
Memory devices might include an array of memory cells and a control logic to control access of the array of memory cells, where a memory cell of the array of memory cells might include a first dielectric adjacent a semiconductor, a control gate, a second dielectric between the control gate and the first dielectric, and a charge storage structure between the first dielectric and the second dielectric, wherein the charge storage structure comprises a charge-storage material and a gettering agent.
Claims
1. A memory device, comprising: an array of memory cells; and a control logic to control access of the array of memory cells, wherein the array of memory cells comprises a memory cell comprising: a first dielectric adjacent a semiconductor; a control gate; a second dielectric between the control gate and the first dielectric; and a charge storage structure between the first dielectric and the second dielectric; wherein the charge storage structure comprises a charge-storage material and a gettering agent; and wherein at least a portion of the charge storage structure comprises a ratio of the gettering agent to the charge-storage material that is greater than a stoichiometric amount.
2. The memory device of claim 1, wherein, in the memory cell, the gettering agent comprises a plurality of gettering agents.
3. The memory device of claim 1, wherein the gettering agent comprises an oxygen gettering agent.
4. The memory device of claim 1, wherein the gettering agent is on the charge-storage material and separates the charge-storage material from the second dielectric.
5. The memory device of claim 1, wherein, in the memory cell, the gettering agent comprises an element or compound meeting at least one criteria, under process conditions experienced by the charge-storage material, selected from a group consisting of preferentially reacting with unreacted oxygen over the charge-storage material, pulling reacted oxygen away from an oxidized charge-storage material, further reacting with oxidized charge-storage material to produce a compound that is conductive, and further reacting with oxidized charge-storage material to produce a dielectric compound that has a higher k value than the oxidized charge-storage material.
6. The memory device of claim 1, wherein, in the memory cell, the gettering agent comprises a metal.
7. The memory device of claim 6, wherein, in the memory cell, the metal is selected from a group consisting of zirconium, beryllium, magnesium, calcium, strontium, scandium, yttrium, rare earth metals, lanthanum, thorium, uranium, hafnium, aluminum and titanium.
8. The memory device of claim 6, wherein, in the memory cell, the gettering agent further comprises a silicide of the metal.
9. The memory device of claim 1, wherein, in the memory cell, at least a portion of the gettering agent is incorporated into the charge-storage material.
10. The memory device of claim 9, wherein, in the memory cell, a concentration of the gettering agent in the charge-storage material is greater nearer the second dielectric than a concentration of the gettering agent in the charge-storage material nearer the first dielectric.
11. The memory device of claim 9, wherein, in the memory cell, the charge-storage material is devoid of the gettering agent in a portion nearer the first dielectric.
12. The memory device of claim 1, wherein the memory device further comprises: an address register for latching received address signals; a command register for latching received command signals; a row decode circuitry for decoding the address signals latched in the address register; and a column decode circuitry for decoding the address signals latched in the address register; wherein the control logic of the memory device is configured to control access of the array of memory cells in response to the command signals latched in the command register, and is further configured to control the row decode circuitry and the column decode circuitry in response to the address signals latched in the address register for access of the array of memory cells.
13. A memory device, comprising: an array of memory cells; and a control logic to control access of the array of memory cells, wherein the array of memory cells comprises a memory cell comprising: a first dielectric adjacent a semiconductor; a control gate; a second dielectric between the control gate and the first dielectric; and a charge storage structure between the first dielectric and the second dielectric; wherein the charge storage structure comprises a silicon-containing material and a metal; and wherein at least a portion of the charge storage structure comprises a ratio of the metal to the silicon-containing material that is greater than a stoichiometric amount.
14. The memory device of claim 13, wherein the memory device further comprises: an address register for storing a received address; and a command register for storing a received command; wherein the control logic of the memory device is configured to control access of the array of memory cells in response to the command stored in the command register and the address stored in the address register.
15. The memory device of claim 13, wherein, in the memory cell, the metal comprises a plurality of different metal elements.
16. The memory device of claim 15, wherein, in the memory cell, a concentration of the plurality of different metal elements in the silicon-containing material is greater than or equal to 1E19/cm.sup.3.
17. The memory device of claim 16, wherein, in the memory cell, the concentration of the plurality of different metal elements is greater than 50 atomic percent.
18. A memory device, comprising: an array of memory cells; and a control logic to control access of the array of memory cells, wherein the array of memory cells comprises a memory cell comprising: a first dielectric adjacent a semiconductor; a control gate; a second dielectric between the control gate and the first dielectric; and a charge storage structure between the first dielectric and the second dielectric; wherein the charge storage structure comprises polysilicon and a metal silicide; and wherein the charge storage structure further comprises an unreacted elemental metal incorporated therein.
19. The memory device of claim 18, wherein at least a portion of the metal silicide is incorporated into the polysilicon.
20. The memory device of claim 18, wherein, in the memory cell, no portion of the polysilicon is in contact with the second dielectric.
21. The memory device of claim 18, wherein the memory device further comprises: an input/output (I/O) control circuitry; an I/O bus for communication of command signals, address signals and/or data signals from an external device to the I/O control circuitry; and a control link for communication of control signals from the external device to the control logic.
22. A memory device, comprising: an array of memory cells; and a control logic to control access of the array of memory cells, wherein the array of memory cells comprises a memory cell comprising: a first dielectric adjacent a semiconductor; a control gate; a second dielectric between the control gate and the first dielectric; and a charge storage structure between the first dielectric and the second dielectric; wherein the charge storage structure consists essentially of a metal silicon oxide and at least one component selected from a group consisting of a metal silicide, a metal oxide and an unreacted metal.
23. The memory device of claim 22, wherein the at least one component separates the metal silicon oxide from the second dielectric.
24. A memory device, comprising: an array of memory cells; and a control logic to control access of the array of memory cells, wherein the array of memory cells comprises a memory cell comprising: a first dielectric adjacent a semiconductor; a control gate; a second dielectric between the control gate and the first dielectric; and a charge storage structure between the first dielectric and the second dielectric; wherein the charge storage structure consists essentially of a metal silicide and at least one component selected from a group consisting of a metal silicon oxide, a metal oxide and an unreacted metal; and wherein at least a portion of the at least one component is incorporated into the metal silicide.
25. A memory device, comprising: an array of memory cells; and a control logic to control access of the array of memory cells, wherein the array of memory cells comprises a memory cell comprising: a first dielectric adjacent a semiconductor; a control gate; a second dielectric between the control gate and the first dielectric; and a charge storage structure between the first dielectric and the second dielectric; wherein the charge storage structure comprises a charge-storage material, a reaction product of a metal and the charge-storage material, and unreacted instances of the metal.
26. The memory device of claim 25, wherein, in the memory cell, the charge storage structure further comprises: a first instance of the charge-storage material; a second instance of the charge-storage material between the first instance of the charge-storage material and the second dielectric; a first instance of the reaction product of the metal and the charge-storage material between the first instance of the charge-storage material and the second instance of the charge-storage material; a second instance of the reaction product of the metal and the charge-storage material between the second instance of the charge-storage material and the second dielectric; a first unreacted instance of the metal between the first instance of the reaction product of the metal and the charge-storage material, and the second instance of the charge-storage material; and a second unreacted instance of the metal between the second instance of the reaction product of the metal and the charge-storage material, and the second dielectric.
27. The memory device of claim 26, wherein, in the memory cell, the second instance of the charge-storage material is thinner than the first instance of the charge-storage material, and wherein the second unreacted instance of the metal is thicker than the first unreacted instance of the metal.
28. The memory device of claim 26, wherein, in the memory cell, the second instance of the charge-storage material is thinner than the first instance of the charge-storage material, and wherein the second unreacted instance of the metal and the first unreacted instance of the metal are a same thickness.
29. The memory device of claim 26, wherein, in the memory cell, the second instance of the charge-storage material and the first instance of the charge-storage material are a same thickness, and wherein the second unreacted instance of the metal is thicker than the first unreacted instance of the metal.
30. The memory device of claim 26, wherein the memory device further comprises: an address register for storing a received address; and a command register for storing a received command; wherein the control logic of the memory device is configured to control access of the array of memory cells in response to the command stored in the command register and the address stored in the address register.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(8) In the following detailed description, reference is made to the accompanying drawings that form a part hereof, and in which is shown, by way of illustration, specific embodiments. In the drawings, like numerals describe substantially similar components throughout the several views. Other embodiments may be utilized and structural, logical, and electrical changes may be made without departing from the scope of the present disclosure. The term semiconductor can refer to, for example, a layer of material, a wafer, or a substrate, and includes any base semiconductor structure. Semiconductor is to be understood as including silicon on sapphire (SOS) technology, silicon on insulator (SOI) technology, thin film transistor (TFT) technology, doped and undoped semiconductors, epitaxial layers of a silicon supported by a base semiconductor structure, as well as other semiconductor structures well known to one skilled in the art. Furthermore, when reference is made to a semiconductor in the following description, previous process steps may have been utilized to form regions/junctions in the base semiconductor structure. The following detailed description is, therefore, not to be taken in a limiting sense.
(9) Traditional floating gate NAND flash structures often use a thick polysilicon (sometimes referred to as polycrystalline silicon) floating gate which can have the control gate wrapped around it, allowing it to program and erase with a silicon dioxide intergate dielectric on the polysilicon. However, this geometry may soon be impracticable to sustain in smaller devices because there may not be enough room to wrap the intergate dielectric and control gate around the polysilicon floating gate. Using this same materials stack in a planar geometry is generally unsatisfactory and may even fail to program. To address this issue, an intergate dielectric using a high-k dielectric may be required. These high-k dielectrics are primarily oxides, and depositing these oxides on polysilicon can oxidize the polysilicon, reducing its ability to function as a charge storage structure.
(10) Various embodiments include memory cells having a charge storage structure between a first dielectric, e.g., a tunnel dielectric, and a second dielectric, e.g., an intergate dielectric, and memory devices and systems including such memory cells. Memory cells of this type are often referred to as floating-gate memory cells or charge trap memory cells. Charge storage structures of various embodiments include a charge-storage material and a gettering agent. As used herein, a gettering agent is an element or compound that is expected, in the case of unreacted oxygen, to preferentially react with that oxygen over the charge-storage material under the process conditions experienced by that charge-storage material; or that is expected, in the case of oxidized charge-storage material, to either pull the reacted oxygen away from the oxidized charge-storage material or to further react with the oxidized charge-storage material to produce a compound that is either conductive or is a dielectric compound having a higher k value than the oxidized charge-storage material. Some gettering agents may meet only one of these criteria, while others may meet more than one of these criteria. Such memory cells are useful in non-volatile memory devices.
(11) Various embodiments use gettering agents to mitigate the oxidation risk of a charge-storage material of a charge storage structure. For example, metal doping and silicidation of a silicon-containing charge-storage material provides such gettering agents, e.g., metal silicides. For one or more embodiments, the metals incorporated into the charge-storage material thermodynamically react with SiO.sub.2 to form either MSiOx (M=metal) or MOx+Si. For example, the elements used to getter oxygen from silicon may do so because their reaction products will have a lower Gibbs Free Energy than SiO.sub.2, and high temperatures supplied during gate stack anneals, e.g., often over 900 C., may overcome the kinetic barriers that would prevent these reactions from occurring. Examples of metals that are theoretically known to work are zirconium (Zr), beryllium (Be), and magnesium (Mg). Additional metals which are expected to work are calcium (Ca), strontium (Sr), scandium (Sc), yttrium (Y), the rare earth metals (e.g. lanthanum (La)), thorium (Th), uranium (U), hafnium (Hf), and aluminum (Al). Beyond these theoretically functional metals, there is experimental evidence in the literature that other metals, such as titanium (Ti), will thermodynamically remove oxygen from silicon.
(12) Such metals doped into a thin polysilicon floating gate could enable integration of the thin polysilicon floating gate with other oxide based materials by acting as an in situ getter for oxygen that is exposed to the polysilicon. As the oxygen reaches the polysilicon, it may either be preferentially bound to the doping metal, or if it does react with silicon to form SiO.sub.2, later, during integration and high temperature anneals, a metal element may diffuse to the SiO.sub.2 site, and pull the oxygen away from the Si to form MOx (metal oxide) or MSiOx (metal silicon oxide).
(13) Having the oxygen bound to the metal accrues multiple benefits. Continuing the example of a polysilicon floating gate, one benefit is that it helps to ensure there is enough silicon to function as a charge storage structure. If too much of the silicon is oxidized, then the silicon may no longer function effectively as a floating gate. A second concern is that SiO.sub.2 is a low-k dielectric which can add significant equivalent oxide thickness (EOT) to the gate stack. The voltage that is available to these gate stacks may be severely limited and this additional amount of EOT can cause additional amounts of voltage to be required to program and erase the charge storage structure and can make these devices unsuitable for memory products. Many of the described metals have oxides whose dielectric constants are high, e.g. HfO.sub.2 has k=20 and TiO.sub.2 has k=80. By converting the oxide from SiO.sub.2, where k=3.9, to a high-k oxide, the EOT of the stack would be reduced.
(14) One additional benefit of metal doping or silicidation of a polysilicon floating gate is that doping such thin polysilicon materials can be quite challenging. Additionally, even if such thin polysilicon materials were to be doped, the dopant species may diffuse out during thermal cycling. Metals described herein generally would not diffuse as easily and may still be available to ensure a sufficient number of electrons are available in the charge storage structure for proper program and erase functions.
(15) Various embodiments incorporate into or on top of the charge-storage material a component that intrinsically scavenges oxygen while prior strategies relied on a barrier layer to prevent the charge-storage material from being exposed to an oxidant. The problem with such prior solutions is that layers of typical gate stacks will oxidize to some degree and such layers are generally permeable to oxygen at some level, increasing the risk that the charge-storage material will eventually become oxidized from available oxygen within the gate stack, thus degrading the cell stack EOT and degrading the electrical properties of the charge-storage material itself. By accepting the likely inevitability of oxygen reaching the charge-storage material, and by incorporating an element in the charge-storage material that will react with the oxygen and remove or inhibit the formation of undesirable oxidation products in situ, e.g., SiO.sub.2 from a silicon-containing charge-storage material, improvements over prior solutions may be facilitated.
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(17) Memory device 100 includes an array of memory cells 104 logically arranged in rows and columns. At least one memory cell of the array of memory cells 104 includes a charge storage structure in accordance with an embodiment of the disclosure. Although various embodiments will be described primarily with reference to NAND memory arrays, the various embodiments are not limited to a specific architecture of the memory array 104. Some examples of other array architectures suitable for the present embodiments include NOR arrays, AND arrays or other arrays.
(18) A row decode circuitry 108 and a column decode circuitry 110 are provided to decode address signals. Address signals are received and decoded to access memory array 104. Memory device 100 also includes input/output (I/O) control circuitry 112 to manage input of commands, addresses and data to the memory device 100 as well as output of data and status information from the memory device 100. An address register 114 is coupled between I/O control circuitry 112 and row decode circuitry 108 and column decode circuitry 110 to latch the address signals prior to decoding. A command register 124 is coupled between I/O control circuitry 112 and control logic 116 to latch incoming commands. Control logic 116 controls access to the memory array 104 in response to the commands and generates status information for the external processor 130. The control logic 116 is coupled to row decode circuitry 108 and column decode circuitry 110 to control the row decode circuitry 108 and column decode circuitry 110 in response to the addresses.
(19) Control logic 116 is also coupled to a cache register 118. Cache register 118 latches data, either incoming or outgoing, as directed by control logic 116 to temporarily store data while the memory array 104 is busy writing or reading, respectively, other data. During a write operation, data is passed from the cache register 118 to data register 120 for transfer to the memory array 104; then new data is latched in the cache register 118 from the I/O control circuitry 112. During a read operation, data is passed from the cache register 118 to the I/O control circuitry 112 for output to the external processor 130; then new data is passed from the data register 120 to the cache register 118. A status register 122 is coupled between I/O control circuitry 112 and control logic 116 to latch the status information for output to the processor 130.
(20) Memory device 100 receives control signals at control logic 116 from processor 130 over a control link 132. The control signals may include a chip enable CE #, a command latch enable CLE, an address latch enable ALE, and a write enable WE #. Memory device 100 receives command signals (which represent commands), address signals (which represent addresses), and data signals (which represent data) from processor 130 over a multiplexed input/output (I/O) bus 134 and outputs data to processor 130 over I/O bus 134.
(21) Specifically, the commands are received over input/output (I/O) pins [7:0] of I/O bus 134 at I/O control circuitry 112 and are written into command register 124. The addresses are received over input/output (I/O) pins [7:0] of bus 134 at I/O control circuitry 112 and are written into address register 114. The data are received over input/output (I/O) pins [7:0] for an 8-bit device or input/output (I/O) pins [15:0] for a 16-bit device at I/O control circuitry 112 and are written into cache register 118. The data are subsequently written into data register 120 for programming memory array 104. For another embodiment, cache register 118 may be omitted, and the data are written directly into data register 120. Data are also output over input/output (I/O) pins [7:0] for an 8-bit device or input/output (I/O) pins [15:0] for a 16-bit device.
(22) It will be appreciated by those skilled in the art that additional circuitry and signals can be provided, and that the memory device of
(23) Additionally, while specific I/O pins are described in accordance with popular conventions for receipt and output of the various signals, it is noted that other combinations or numbers of I/O pins may be used in the various embodiments.
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(25) As shown in
(26) Memory array 200 includes NAND strings 206.sub.1 to 206.sub.M. Each NAND string includes transistors 208.sub.1 to 208.sub.N, each located at an intersection of a word line 202 and a bit line 204. The transistors 208, depicted as floating-gate transistors in
(27) A source of each source select gate 210 is connected to a common source line 216. The drain of each source select gate 210 is connected to the source of the first floating-gate transistor 208 of the corresponding NAND string 206. For example, the drain of source select gate 210.sub.1 is connected to the source of floating-gate transistor 208.sub.1 of the corresponding NAND string 206.sub.1. A control gate of each source select gate 210 is connected to source select line 214. If multiple source select gates 210 are utilized for a given NAND string 206, they would be coupled in series between the common source line 216 and the first floating-gate transistor 208 of that NAND string 206.
(28) The drain of each drain select gate 212 is connected to a local bit line 204 for the corresponding NAND string at a drain contact. For example, the drain of drain select gate 212.sub.1 is connected to the local bit line 204.sub.1 for the corresponding NAND string 206.sub.1 at a drain contact. The source of each drain select gate 212 is connected to the drain of the last floating-gate transistor 208 of the corresponding NAND string 206. For example, the source of drain select gate 212.sub.1 is connected to the drain of floating-gate transistor 208.sub.N of the corresponding NAND string 206.sub.1. If multiple drain select gates 212 are utilized for a given NAND string 206, they would be coupled in series between the corresponding bit line 204 and the last floating-gate transistor 208.sub.N of that NAND string 206.
(29) Typical construction of floating-gate transistors 208 includes a source 230 and a drain 232, a floating gate 234 as a charge storage structure, and a control gate 236, as shown in
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(31) As further depicted in
(32) Formation of the structure of
(33) The charge storage structure 315 is then formed over the tunnel dielectric 310. Formation of the charge storage structure 315 will be described in more detail with reference to
(34) The intergate dielectric 320 is then formed over the charge storage structure 315. The intergate dielectric 320 is generally one or more dielectric materials. For example, the intergate dielectric 320 may include one or more layers of dielectric materials including high K dielectric materials. Example high-k dielectric materials for intergate dielectric 320 include aluminum oxides (AlOx), hafnium oxides (HfOx), hafnium aluminum oxides (HfAlOx), hafnium silicon oxides (HfSiOx), lanthanum oxides (LaOx), tantalum oxides (TaOx), zirconium oxides (ZrOx), zirconium aluminum oxides (ZrAlOx), yttrium oxide (Y.sub.2O.sub.3), etc. For one embodiment, the intergate dielectric 320 includes an ozone-based formation of hafnium silicon oxide followed by water-based formation of hafnium oxide. For a further embodiment, the intergate dielectric 320 includes a high-k dielectric material over silicon nitride.
(35) The control gate 325 is formed over the intergate dielectric 320. In general, the control gate 325 includes one or more conductive materials. For one embodiment, the control gate 325 contains a conductively-doped polysilicon. For another embodiment, the control gate 325 contains a metal-containing material. For a further embodiment, the control gate 325 includes a metal-containing material over polysilicon, e.g., a refractory metal silicide formed on a conductively-doped polysilicon. The metals of chromium (Cr), cobalt (Co), hafnium (Hf), molybdenum (Mo), niobium (Nb), tantalum (Ta), titanium (Ti), tungsten (W), vanadium (V), zirconium (Zr), and metal nitrides (including, for example, titanium nitride, tantalum nitride, tantalum carbon nitride, tungsten nitride) for metal gates are generally recognized as refractory metal materials. For another embodiment, the control gate 325 contains multiple metal-containing materials, e.g., a titanium nitride (TiN) barrier over the intergate dielectric 320, titanium (Ti) as an adhesion material over the barrier, and tungsten (W) over the adhesion material.
(36) The dielectric cap 330 can be formed over the control-gate 325 to act as an insulator and barrier layer to protect the control gate 325 during subsequent processing. The dielectric cap 330 contains one or more dielectric materials and may include, for example, such dielectrics as silicon oxides (SiOx), silicon nitride (SiNx), and silicon oxynitrides (SiOxNy). For one embodiment, the dielectric cap 330 is a silicon nitride, formed, for example, by such methods as CVD. It is noted that additional layers may be used to form the gate stack, such as barrier materials to inhibit diffusion between opposing materials or adhesion materials to promote adhesion between opposing materials.
(37) In
(38) Following this patterning of the mask 335, exposed portions of the dielectric cap 330 and underlying portions are removed in
(39) In
(40) In
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(42) For one embodiment, the charge-storage material 450 has a thickness of approximately 10 to 100 (1 nm to 10 nm). For a further embodiment, the charge-storage material 450 has a thickness of approximately 30 to 50 (3 nm to 5 nm). It is recognized that the variability of industrial fabrication will inherently produce minor variations in thickness such that a process seeking a particular thickness, e.g., 30 (3 nm), will likely produce thicknesses cell-to-cell that are above and below that particular value.
(43) In
(44) The concentration of the metals 455 may be a gradient across the charge-storage material 450, or it may be uniform across the charge-storage material 450.
(45) For certain embodiments, at least some of the charge-storage material 450 is formed to be substantially devoid (e.g., devoid) of metals 455. For example, polysilicon may be devoid of metals as formed.
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(47) In the example depicted in
CONCLUSION
(48) Memory cells including a charge storage structure having one or more gettering agents can be useful in non-volatile memory devices. Various embodiments provide for gettering of oxygen from a charge-storage material of the charge storage structure to facilitate a mitigation of detrimental oxidation of the charge-storage material.
(49) Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement that is calculated to achieve the same purpose may be substituted for the specific embodiments shown. Many adaptations of the embodiments will be apparent to those of ordinary skill in the art. Accordingly, this application is intended to cover any adaptations or variations of the embodiments.