JOURNAL OF APPLIED PHYSICS

VOLUME 84, NUMBER 10

15 NOVEMBER 1998

Nonvolatile memory effects in nitrogen doped tetrahedral amorphous carbon thin lms
E. G. Gerstnera) and D. R. McKenzie
School of Physics, University of Sydney, New South Wales 2006, Australia

Received 21 April 1998; accepted for publication 20 August 1998 Electrical measurements of nitrogen doped tetrahedral amorphous carbon ( ta -C:N thin lms have revealed a reversible nonvolatile memory effect, related to the excitation and de-excitation of electrons between deep acceptor states and shallow donor states within the mobility gap. This effect is characterized by changes in the small signal lm conductivity of up to 10 times, and has been used to fabricate 1-bit memory cells with effective memory retention times in the order of several months. 1998 American Institute of Physics. S0021-89799805522-4

I. INTRODUCTION

Electron states located within the band gap of a semiconductor are normally detrimental to its performance as they act as traps for mobile carriers. In this article we show that these states can act as a means of storing binary information in a nonvolatile manner and may therefore form the basis for potential memory devices. Furthermore, we show that these memory effects, observed in nitrogen doped tetrahedral amorphous carbon thin lms, are a new phenomenon brought about by a switching between two electrical states in which different conduction mechanisms dominate: a high resistance state in which hopping conduction dominates; and a low resistance state in which PooleFrenkel conduction1 dominates. Amorphous carbon thin lms with a high tetrahedral content are produced by condensation onto a substrate from energetic carbon ion uxes.2 The properties and formation of this material, referred to as tetrahedral amorphous carbon ( ta -C, have recently been reviewed.3 In a material of high sp 3 a band gap of approximately 2.5 eV opens up between the residual and * states. Ta -C is weakly p type,4 and can be doped n type by the incorporation of phosphorus or nitrogen.5 With the emergence of improved thin-lm deposition technologies during the late 1960s and early 1970s, there appeared in the literature several reports on the observation of memory effects in various amorphous insulators and semiconductors. The bulk of these can be classed into two different categories of current- and voltage-controlled effects, depending on the mechanism by which switching between states occurs. Ovonic switching, reported by Ovshinsky et al.6 in chalcogenide glasses is probably the best known of current-controlled effects. This type of switching is believed to occur by a current controlled transition between a high conductivity polycrystalline and a low conductivity amorphous phase of the material see Mott and Davis.7 The second category of voltage-controlled switching has been reported in a range of insulating oxide, sulde, and uoride thin lms810 and has been reviewed by Simmons
a

and Verderber.11 This type of switching is typied by a reduction in resistance after the application and rapid removal within 0.1 ms of voltage bias beyond some threshold, with the low resistance state persisting until the bias again exceeds the threshold and removed more gradually 0.1 ms. The operation of both current- and voltage-controlled effects are symmetric with respect to the direction of bias. The effect on which we report here lies in the voltage-controlled category, however, the direction of bias plays a critical role in the switching process. We therefore consider it to be a new type of effect, qualitatively different to those previously observed in other amorphous materials. Currently, the majority of commercial nonvolatile memories operate by the storage of electrons in the charge traps of a oating silicon nitride gate, by either hot electron injection or tunnelling across a thin silicon dioxide lm.12 The gate is usually embedded between the channel and the gate of a metal oxide semiconductor eld effect transistor MOSFET, with the charge state of a cell measured by testing the turn-on voltage of the FET. The disadvantages of such metal-nitride-oxide-silicon MNOS technology are low information density, fabrication complexity, and expense. Conversely, the simplicity of the structure of ta -C memory cells suggests the potential for overcoming these disadvantages.
II. EXPERIMENT

Electronic mail: eddie@physics.usyd.edu.au 5647

Nitrogen doped ta -C denoted ta -C:N thin lms were deposited by means of a ltered cathodic vacuum arc onto aluminum lms which had been thermally evaporated onto both glass and silicon substrates. Nitrogen was incorporated into these lms by the introduction of nitrogen gas into the vacuum chamber during deposition. The lms studied here were deposited with nitrogen base pressures of between 10 4 and 10 3 Torr, with optimal results occurring at 6 10 4 Torr. The nitrogen ow rates required to maintain these pressures were between 2 and 12 standard cubic centimeters per minute sccm. The atomic concentration of nitrogen in these lms was found to be approximately 5%, measured using electron energy loss spectroscopy. The substrates were water cooled to keep them at room temperature during deposition,
1998 American Institute of Physics

0021-8979/98/84(10)/5647/5/$15.00

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5648

J. Appl. Phys., Vol. 84, No. 10, 15 November 1998

E. G. Gerstner and D. R. McKenzie

FIG. 1. I V characteristic of a ta -C:N memory cellarrows indicate the direction of voltage sweep sweep rate 0.83 V/s. Dotted line represents a symmetric projection of the forward swept reverse characteristic to positive voltages to highlight the transition from the low to the high resistance state with forward bias.

FIG. 2. Small signal resistance of a ta -C:N memory cell as a function of pulse amplitude for a 100 s negative voltage pulse. The device was erased between write pulses with a positive erase bias.

and no substrate bias was applied. The thickness of the lms lay was between 50 and 100 nm. The lms were transparent and displayed strong interference colors indicating a relatively small optical absorption. The conductivity of the lms was approximately 6 10 4 cm. All electrical measurements were made through lm of sandwich structures of ta -C:N lms between a sprung gold point contact on the surface, and an underlying aluminum lm. A Hewlett Packard HP4145b semiconductor parameter analyzer was used to collect the currentvoltage characteristics. The area of contact between the top contact and the surface of the ta -C:N lm was approximately 10 3 mm2 . The biases quoted are those of the top contact with respect to the underlying contact.

III. RESULTS AND DISCUSSION A. Switching in ta -C:N lms

We rst observed memory effects in ta -C in the currentvoltage I V ) characteristics of ta -C:N lms. When collecting the through lm I - V characteristics between a sprung gold point contact and an underlying thin lm aluminum contact, a kink in the forward direction positive bias of the point contact was observed see Fig. 1. In the reverse direction passing from positive to negative biases this kink was then found to disappear. Further investigation revealed that the kink in the forward part of the I V characteristic only appeared after the application of a certain negative threshold bias, and disappeared after the application of a certain positive threshold bias. In other words, the device had a memory of whether a negative or a positive bias had been applied to it, by the presence or absence respectively of a kink in the forward I V curve. Furthermore it was found that upon the application of a negative voltage pulse beyond some threshold amplitude herein referred to as the write bias, the small signal resistance measured at voltages 0.5 V decreased by a factor of between 5 and 10 times see Fig.

2, which could be reversed simply by the application of a positive pulse of similar amplitude the erase bias. It is the transition from the high conductivity state to the low conductivity state with the application of bias above a given positive voltage which causes the kink in the forward characteristic. By extending the I V characteristic of the high conductivity state at negative bias to be symmetrical at positive bias the dotted line in Fig. 1 this transition is clearly illustrated. It should be noted that the transition from the high to the low resistance states is not due to electrical avalanche breakdown of the material. Such breakdown of the material can occur at voltages around twice those used here, however the resulting resistance afterwards is of the order of 100 times lower than that after the application of a negative write bias. When voltages well below either the write or erase thresholds were applied to a device, no noticeable change occurred in the state of the device. As a result, small voltages can be used to test the resistance of a device without affecting the state, providing a method of reading a device nondestructively. We can therefore write a 1 or ON with a negative threshold bias, erase this to 0 or OFF with positive threshold bias, and read the state by measuring the resistance with a small bias between these thresholds. Furthermore, the ON low resistivity state of the device was found to persist for extended periods of time see Sec. III C.
B. Conduction mechanisms

In order to investigate the switching mechanism and its temperature dependence, a device was cycled between its ON and OFF state at various temperatures between 40 and 360 K. Switching between states was achieved with write and erase voltages of 3 and 3 V, respectively. In order to avoid changing the state during measurement, ON currents were collected at negative biases after writing, and OFF currents at positive biases after erasing. Arrhenius plots of the currents versus inverse temperature were then plotted at various biases see Fig. 3. At temperatures much below 250 K no measurable change in the memory state was observed.

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J. Appl. Phys., Vol. 84, No. 10, 15 November 1998

E. G. Gerstner and D. R. McKenzie

5649

when unoccupied which lie just below the conduction band edge. The activation energy for PooleFrenkel conduction at high elds is given by,1 E a E i V / t 1/2, 1

FIG. 3. The current in the ON points and OFF lines states of a memory device as a function of 1/T , at different applied voltages.

At such temperatures, conduction mechanisms present in both the OFF and ON states dominate, allowing no discrimination between the two conduction states. At temperatures above 250 K, however, signicant differences between the ON and OFF state, in both the temperature and voltage dependence of the conductivity, were found, reecting the dominance of different conduction mechanism in each of the two states. In the OFF state, the conductivity exhibited a weak temperature dependence, with an activation energy of 0.07 0.01 eV which was independent of bias. Conduction in this state is expected to proceed via hopping between states near the Fermi energy, as occurs in many amorphous semiconductors.13 Conversely, in the ON state, the conductivity was found to have a stronger dependence on temperature, with a voltage dependent activation energy decreasing linearly with the square root of the applied bias see Fig. 4, consistent with single center PooleFrenkel conduction.1 Such conduction occurs by the eld assisted thermionic emission of electrons from donor traps positively charged

FIG. 4. The activation energy for conduction in a device in the ON state as a function of V 1/2, calculated from the temperature dependence shown in Fig. 3. The linear dependence of E a with respect to V 1/2 is indicative of single center PooleFrenkel conduction Ref. 1.

where E i is the activation energy at zero eld, is the PooleFrenkel constant for the material, t is the lm thickness, and V is the applied voltage. Therefore, using Eq. 1 and extrapolating the voltage dependence in the ON state to zero eld an activation energy of E i 0.25 eV is found, and represents the position of the donor states below the conduction band edge. With these two conduction mechanisms in mind it therefore appears that switching to the ON state proceeds by the promotion of electrons held in deep acceptor traps to shallower unoccupied donor traps 0.25 eV below the conduction band, with the increase in conductivity due simply to the greater efciency of PooleFrenkel conduction which emits electrons to the extended states of the conduction band, as opposed to hopping conduction comprising transitions between localized states at the Fermi level. The very slow decay of the ON state is explained by the fact that the rate of direct transitions from donor states to acceptor states deeper in the gap will be very low as they are between extremely localized states as opposed to other trap related processes such as carrier recombination in which at least one of the states is extended. Furthermore, it is expected that the rate of capture of electrons from the conduction band is greater for unoccupied donor traps than for unoccupied acceptor traps, owing to the positive coulombic attraction associated with only the donor traps. With respect to nitrogen doping of ta -C, the lling of deeper acceptor states by the decay of electrons from nitrogen donor states just below the conduction band, explains both the movement of the Fermi energy with increased nitrogen doping and the poor doping efciency observed by Amaratunga et al.4,14 The write process in the above model is analogous to the creation of a population inversion in a laser. In the high resistance ground state the majority of donor electrons will be held in acceptor traps deep within the mobility gap, with the majority of donor states being ionized. In the lower resistance state some number of the donor states are relled, representing a nonequilibrium excited state of the material. Herein, we present a possible explanation for the bias dependent switching between the two states. We rst assume a situation in which the top contact is more rectifying than the bottom contact, as in the case with many other ntype semiconductors with Au and Al contacts, and then consider the effect of a negative write bias on the region directly underneath the top contact. Band bending will cause this region to be forced into depletion, and any electrons which undergo thermionic emission to the conduction band will be immediately swept from the region. This will cause a net ionization of electrons from acceptor traps in the region see Fig. 5a. When the voltage is removed the excess electrons will be recaptured preferentially by positively charged, unoccupied donor traps 0.25 eV below the conduction band edge as determined from the voltage dependence of the activation energy in the ON state, resulting in a metastable

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J. Appl. Phys., Vol. 84, No. 10, 15 November 1998

E. G. Gerstner and D. R. McKenzie

FIG. 6. Resistance of a ta -C:N memory cell as a function of time after a 2.8 V write pulse of 5 ms duration. The solid line represents a leastsquares t of Eq. 2 to the experimental data.

R t R ON

R OFF R ON

R 1 t / t 0 m 1R

FIG. 5. Write and erase processes of a ta -C:N memory cella a net ionization of electrons from acceptor traps (D ) is achieved by the depletion of electrons from the region directly underneath the top contact, these electrons are then recaptured by positively charged donor traps D ), and b a net recapture of electrons is achieved by the accumulation of electrons in the region underneath the top contact.

population inversion of electrons higher in the mobility gap, and more importantly, above the Fermi energy. It should be noted that given the dimensions of the thin lm 100 nm, and its insulating nature, the region of depletion can extend well into the bulk of the lm under conditions of signicant bias. Turning now to the erase process, a positive bias applied to the top contact will accumulate electrons in the region enhancing the lling of all traps throughout the gap see Fig. 5b. When most donor traps are lled acceptor traps will proceed to ll. At the same time a narrow region of positive space charge will form in the metal. Thus, when the applied eld is removed, a eld will be generated so as to neutralize this charge in the metal. Since the electrons held in the shallow donor traps are more mobile than those in deeper acceptor traps, such traps will be emptied before deeper traps, and the distribution will be returned to the OFF state.
C. Memory retention

where R ON is the resistance immediately after writing, R OFF is the resistance when completely erased, R is the tolerance level for distinguishing the ON states resistance of the device from the OFF state, t 0 is the time at which the device decays to this tolerance level, and m is the exponent of decay related to the ON state charge distribution and the temperature. This expression was tted to the experimental data by a leastsquares algorithm with only two free parameters t 0 and m , yielding excellent agreement indicated by the solid line in Fig. 6. If we extend this t to longer times and use a tolerance level of 20% ( R 0.2, the fraction of the total difference between the ON and OFF states, below the OFF state we nd effective retention times in the order of several months. An important question relating to the possible application of this memory effect in the fabrication of commercial devices is the effect of temperature on the rate of memory decay. In a previous article,15 the write and erase currents measured as a function of time at constant bias were found to have a power law dependence. Furthermore, the erase current has a similar form to that of the memory decay, suggesting that the erase and decay processes proceed by similar mechanisms albeit at different rates, with similar temperature dependencies. Therefore by measuring the temperature dependence of the erase current, we can infer the temperature dependence of the memory decay. The expression for the erase current is given by, I discharge t I I 0 At m 3

In order to determine the duration of effective memory retention of the devices a cell was written with a 2.8 V write pulse of width 5 ms, and the small signal resistance monitored at regular intervals over a period of several weeks. The resulting decay prole see Fig. 6 was found to have a power law dependence on time, and is well described by the expression,15

where I is the nal current after the device is completely discharged, I 0 is the initial difference in the current before discharging, A is a constant related to the donor electron emission rate, and m is the time dependence exponent. By collecting erase currents as a function of time at constant erase voltages, at different temperatures, and then tting Eq. 3 to the data, the temperature dependencies of the coef-

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J. Appl. Phys., Vol. 84, No. 10, 15 November 1998

E. G. Gerstner and D. R. McKenzie

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time between 293 and 360 K. The implication for the memory retention is that at 310 K the decay proceeds at approximately twice the rate of that at room temperature.
IV. CONCLUSION

FIG. 7. Erase coefcients A and m obtained from least squares ts of Eq. 3 to erase current data collected at various temperatures.

cients m and A can be found. The results see Fig. 7 indicate a linear relationship with temperature for both coefcients, with m increasing and A decreasing with increasing temperature. From these, the time to erase the device can be calculated here dened as the time to reduce the conductivity of the device to within 20% of its OFF state value. The results see Fig. 8 give a relatively weak exponential dependence on temperature, with around a ten times decrease in the erase

A memory effect which involves switching between high and low resistance states in nitrogen doped tetrahedral amorphous carbon thin lms has been observed. The two states are characterized by two different dominant conduction mechanisms: in the high resistance state by hopping conduction via states near the Fermi level within the mobility gap; and, in the low resistance state by PooleFrenkel conduction from donor states 0.25 eV below the conduction band edge. Switching is believed to involve the promotion of electrons from acceptor states deep in the gap to higher donor states, and a mechanism by which this may occur has been proposed. Furthermore, switching is found to be critically dependent on the direction of applied bias, distinguishing it apart from other voltage-controlled memory effects reported previously in other amorphous semiconductors in the literature. The 1-bit memory cells were fabricated with write times down to 100 s and effective memory retention in the order of several months, opening the possibility for the use of this effect as a means of nonvolatile digital information storage.
R. M. Hill, Philos. Mag. 23, 59 1971. D. R. McKenzie, D. A. Muller, and B. A. Pailthorpe, Phys. Rev. Lett. 67, 773 1991. 3 D. R. McKenzie, Rep. Prog. Phys. 59, 1611 1996. 4 G. A. J. Amaratunga, D. E. Segal, and D. R. McKenzie, Appl. Phys. Lett. 59, 69 1991. 5 D. R. McKenzie, D. A. Muller, B. A. Pailthorpe, Z. H. Wang, E. Kravtchinskaia, D. Segal, P. B. Lukins, P. D. Swift, P. J. Martin, G. A. J. Amaratunga, P. H. Gaskell, and A. Saeed, Diamond Relat. Mater. 1, 51 1991. 6 S. R. Ovshinsky, Phys. Rev. Lett. 21, 450 1968. 7 N. F. Mott and E. A. Davis, in Electronic Processes in Non-Crystalline Materials, 2nd ed. Clarendon, Oxford, 1979, Chap. 9, pp. 507512. 8 G. S. Kreynina, Radio Eng. Electron. Phys. 7, 1949 1962. 9 T. W. Hickmott, J. Appl. Phys. 36, 1885 1965. 10 J. G. Simmons and R. R. Verderber, Radio Electron. Eng. 34, 81 1967. 11 J. G. Simmons and R. R. Verderber, Proc. R. Soc. London, Ser. A 301, 77 1967. 12 H. E. Maes, G. Groeseneken, H. Lebon, and J. Witters, Microelectron. J. 20, 9 1989. 13 N. F. Mott and E. A. Davis, Electronic Processes in Non-Crystalline Materials, 2nd ed. Clarendon, Oxford, 1979. 14 G. A. J. Amaratunga, V. Veerasamy, W. I. Milne, and D. R. McKenzie, 2nd International Conference on Applications of Diamond Films and Related Materials MYU, Tokyo, 1993. 15 E. G. Gerstner and D. R. McKenzie, Diamond Relat. Mater. to be published.
1 2

FIG. 8. Erase time to reduce the conductivity of a device to within 20% of its OFF state, as a function of temperature, as calculated from value for A and m obtained from least squares ts of Eq. 3 to erase current data collected at various temperatures.

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