The ion implantation-induced properties of one-dimensional nanomaterials
© Li et al.; licensee Springer. 2013
Received: 26 January 2013
Accepted: 18 March 2013
Published: 17 April 2013
Nowadays, ion implantation is an extensively used technique for material modification. Using this method, we can tailor the properties of target materials, including morphological, mechanical, electronic, and optical properties. All of these modifications impel nanomaterials to be a more useful application to fabricate more high-performance nanomaterial-based devices. Ion implantation is an accurate and controlled doping method for one-dimensional nanomaterials. In this article, we review recent research on ion implantation-induced effects in one-dimensional nanostructure, such as nanowires, nanotubes, and nanobelts. In addition, the optical property of single cadmium sulfide nanobelt implanted by N+ ions has been researched.
KeywordsNanomaterials Ion implantation Doping
One-dimensional nanomaterials have been reported plentifully, owing to its fascinating characteristics. One-dimensional nanomaterials, as an important member of the nanomaterial family, have been widely applied in the formation of a nanodevice. In recent years, several research have reported on various one-dimensional nanomaterial-based nanodevices, including field effect transistors (FETs) [1–4], nanogenerators , and solar cells . Compared with conventional devices, nanodevices based on one-dimensional nanomaterials have certain characteristics, including superspeed, superhigh frequency; high integration density; and low power consumption. These characteristics impel one-dimensional nanomaterial-based nanodevices to be a vast potential prospect for future development in nanoelectronics and optoelectronics. All of these embody the excellent properties of one-dimensional nanomaterials. As two-dimensional nanomaterials, thin film materials also have special properties like quantum effect and broadened bandgap. Compared with thin film materials, one-dimensional nanomaterials have a more obvious quantum effect, higher surface energy, and larger surface activity. Nanowires/nanotubes/nanobelts as quasi-one-dimensional nanostructure are ideal building blocks for nanoscale devices.
With the advent of modern times, higher performance devices are desired. In order to get more high-performance devices, the pivotal problem is how to get better quality materials. Generally, we dope some impurities into the materials as a solution. Traditional doping methods can be roughly divided into three classes: doping during growth, doping by diffusion, and ion implantation. Doping with few impurities into one-dimensional nanomaterials has been achieved already, but controllable and reproducible doping is still difficult to be achieved during growth. Ion implantation is an advanced technique that has been widely applied in material surface modification for nearly 30 years. As a method for industrial application, ion implantation is a controllable and rather exact manner. Compared with conventional doping method, the prominent advantage of ion implantation is that almost all elements can be used for implantation and it never draws into any other impurity elements. Lately, focus ion beam (FIB) system has been used to perform ion implantation process [7, 8]. In this method, the position of ion implantation becomes steerable. In this letter, we review literatures on the application of ion implantation on one-dimensional nanomaterials. Finally, we report on our work on the photoluminescence (PL) emission property of single CdS nanobelt implanted by N+ ions. CdS nanobelts have been marked by Au markers. Furthermore, the PL emission spectrum of every marked CdS nanobelts has been recorded before ion implantation. The experiment was designed to study the PL emission variation of the same CdS nanobelt after ion implantation.
The changes of morphology and structure
Damages induced by ion implantation in an irradiated material are very different; they are related to the ion species, energy, fluences, beam current, and target material. All of these factors may impact the amount and type of the produced damage. While at high fluences, nanowires (NWs) have been observed to be bent and even completely amorphous [9, 10]. Under low implantation fluences, it will only create some isolated point defects like vacancies and interstitials. When ions are implanted into the material, collision cascade may occur during the implantation process. Furthermore, this effect may cause abundant defects; a single implanted ion can create tens of thousands of vacancies and interstitials in the target materials . However, most of these damages can be removed instantaneously by dynamic annealing . Generally speaking, the collision has three independent processes, including nuclear collision, electron collision, and charge exchange. Among of these, nuclear collision pertains to elastic collision, and the result is that abundant defects will be created. Electron collision refers to the collision between incident ions and electrons of the target material, and this collision process pertains to an inelastic collision process. During the electron collision process, electrons of target atoms will probably be excited. Another process is the charge exchange between incident ions and target atoms. During this process, incident ions transfer energy to target atoms or electrons of target atoms, and the incident ions will be stopped within the target after multiple impacts.
Another important phenomenon is the sputtering effect. This effect generally impacts the shape and morphology of nanomaterials . During the implantation process, as the collision cascades, induced by incident ions, the atoms of the target material may get enough energy to be ejected out from the target material . On this account, the surface region of the nanowire will be sputtered away. This sputtering effect will be enhanced at low-lying areas, and then the nanowires will become rougher .
Ion implantation not only causes the above-mentioned effects; Dhara et al.  reported that nanowires have a phase transformation after ion implantation. The Ga-implanted GaN nanowires transform from hexagonal phase to cubic phase. They ascribed this effect to two main reasons: one is that the accumulation of Ga ions have reduced the surface energy and stabilized the cubic phase, and the other possible reason is the short-range order fluctuations caused by dynamic annealing during the implantation process.
The effect of the properties caused by ion implantation
When the ions are implanted into the nanomaterials, the ions will collide with the target atoms and charges. As noted previously, the collision processes include three different modes: nuclear collision, electron collision, and charge exchange. Incident ions lose the energy during every collision process and may be stopped within the materials as impurity atoms. It is common that most of these incident ions stay at the interstitial sites, and these interstitial impurities may migrate to substitutional positions after annealing. This substitutional doping enables the nanomaterials to get more admirable properties.
After ion implantation and annealing, the carrier concentration of nanomaterials may increase dramatically and even the conductive type of nanomaterials may be converted by this fierce process. Without annealing, the implanted nanomaterials revealed worse conductivity, attributing to the damaged crystal lattice. In order to recover the crystal lattice, subsequent annealing is essential. On the other hand, annealing also provides the condition to activate impurity atoms.
Owing to the desirable optical properties of semiconductor nanomaterials, many nanomaterials were used to fabricate light-emitting diodes [40–42] and nanowire lasers . However, there are still some imperfections of these nanodevices; doping with optically activated impurities (like transition metals and rare earth elements) through ion implantation may improve the properties of these nanodevices . Transition metals (TM) are interesting doping elements for semiconductor nanowires because of its enormous optical influences to semiconductor nanowires. Doping with rare earth elements is another significant research direction, as rare earth elements have a special outermost electron structure .
There are many other II-VI and III-V semiconductor nanomaterials that deserve to be researched like ZnS, GaN, ZnSe, and CdTe. One-dimensional nanomaterials have also been widely applied in the field of photocatalysis.
Several research about diluted magnetic semiconductor (DMS) have become much more attractive since Dietl et al. predicted that several wide bandgap semiconductors possibly have a room temperature Tc, including GaN and ZnO . Low-dimensional DMS materials like nanowires have a significant application in spintronic nanodevices. The most important assignment is the synthesis of suitable DMS materials. Many papers reported that they can get room-temperature ferromagnetism through TM doping in the semiconductor materials, but some other researchers did not acquire room-temperature ferromagnetism through almost the same method. Ion implantation, as an effective doping method, plays an important role in the preparation of DMS.
GaAs  and GaN [63, 64] as III-IV semiconductors have excellent properties to fabricate DMS; TM-implanted GaN has a high Tc (≧300 K) . So far, the origin of room-temperature ferromagnetism of the TM-implanted DMS was not clear. The low repeatability of room-temperature ferromagnetic semiconductors is another problem.
Nitrogen-implanted single cadmium sulfide nanobelt
Many growth methods have been used to fabricate nanowires; with the development of technology, growth methods become outmoded, and various kinds of nanomaterials are developed. These nanomaterials have been applied in fabricating high-performance electronic or optical devices. With the purpose of getting higher performance devices, various elements were doped into the nanomaterials. Nevertheless, doping is not effortless; p-type doping of certain materials, such as CdS and ZnO, are rather knotty. Obviously, ion implantation is the most accurate and controllable method for doping, and theoretically, ion implantation can be appropriate for almost all the elements. We need not consider solubility limits and never fear to introduce impurity elements. After ion implantation, the electrical conductivity of nanowires can be increased by several orders of magnitude. The p-n junctions can be created in vertically grown nanowires after ion implantation. Ion implantation has also been utilized to fabricate nanoscale electrical devices. Implanted nanowires show a different optical characteristic compared to the as-grown nanowires. After ion implantation, the luminescence spectrum of the nanowires may be broadened and the bandgap will be changed. These properties changed by ion implantation are important in fabricating optical devices. Research on diluted magnetic semiconductor nanowires still has a long way to explore. The origin of room-temperature ferromagnetism should be figured out.
With technological improvements, devices inch toward the mini size; in this situation, accurate doping of nanomaterials becomes significant. Consequently, accurate and effective doping of one-dimensional nanomaterials will be the focus of research. We will focus on this field in the future.
Diluted magnetic semiconductor
Field effect transistor
Focus ion beam
The authors thank the NSFC (11005082, 91026014, 11175133, 51171132,U1260102), the foundations from Chinese Ministry of Education (311003, 20100141120042, 20110141130004 ), NCET (120418), Young Chenguang Project of Wuhan City (201050231055), and the Fundamental Research Funds for the Central Universities, Hubei Provincial Natural Science Foundation (2011CDB270, 2012FFA042).
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