In a Physics Laboratory
The Problem
You are a physicist investigating the properties of semiconductors, which are materials used to make transistors. When you apply a voltage to one specimen of silicon (a semiconductor), it doesn’t behave quite like the others that you’ve studied. The electrical properties of this odd specimen are unusual and interesting and could lead to a new type of transistor. What makes this specimen different from the others? Very small amounts of impurities can cause large changes in the electrical properties of semiconductors. You would like to obtain a chemical analysis of the material, but your colleagues in chemistry tell you they would have to dissolve a good size part of your sample to analyze it and you are reluctant to give it up. How do you do it?
The Solution
You decide to try neutron activation analysis. You realize you won’t be able to detect all the elements, but many of those that might affect semiconductor performance could be detected quite easily.
What will you need? A source of neutrons to activate the material and a gamma-ray spectrometer to measure the radiation from the material afterwards. This spectrometer detects and measures gamma rays and sorts them according to their energy. You find that your friend down the hall, who is a nuclear physicist, has a gamma-ray spectrometer that incorporates a lithium-drifted germanium crystal as a detector and a pulse height analyzer. The germanium detector is a device that senses the gamma rays that enter it and gives electrical signals related to the energy of the gamma rays. It was invented only a few years ago and has a very fine resolution. That is, it can easily “pick out” gamma rays that are only slightly different in energy. For example, for gamma rays with energies of approximately 1 MeV (million electron volts), it is not unusual to distinguish between gamma rays that differ by only 2 or 3 tenths of a percent. The pulse height analyzer is an electronic device that sorts the electrical pulses from the detector according to their energy.
A lithium-drifted germanium-crystal gamma-ray detector. The large container is a reservoir of liquid nitrogen that keeps the detector cooled to a temperature of -196° Centigrade (321° below zero, Fahrenheit). The lead brick shield keeps out most of the gamma rays that come from naturally radioactive materials in the room. The plastic slots hold cards upon which the samples are mounted for counting. Sometimes the detector is arranged vertically and samples are placed on shelves above it.
What about the neutrons for the irradiation? Although there isn’t a suitable nuclear reactor[9] in your city, there is one at a university only an hour away by jet. Since it may take a few hours to get the sample to the counter after irradiation, you won’t be able to look for short-lived activation products, i.e., those with half-lives of up to an hour. However, this will exclude only a few elements from detection.
A pulse-height analyzer used for gamma-ray spectrometry. A gamma-ray spectrum is displayed on the television screen. Data is printed out automatically on the electric typewriter and also may be plotted as a graph on the paper to the left. In other systems, data may be coded onto punched paper tape as well. Such tape may be “read” by a computer that can be programmed to use the data to calculate what radioactive isotopes are present and their quantities.
Now you are ready to begin the analysis. This will be a qualitative analysis since you are merely looking for a significantly different element in that silicon crystal. How much of it is present is only of secondary interest. Therefore, if you find anything different, you will rely on an approximate calculation to tell you “how much”.
This is called a “swimming pool” reactor because the nuclear fuel, built into metal rods, is held in a framework at the bottom of a deep pool of water. The water serves as a shield to protect workers from the radiation and also helps the reactor “go” by slowing down neutrons to make them more likely to interact with the target atoms. “Swimming pool” reactors are frequently used for neutron activation analysis and typically provide neutron fluxes of over 10¹³ (10 million million) neutrons per square centimeter per second.
These sealed quartz capsules contain samples to be irradiated in a nuclear reactor. They are about to be placed in the aluminum can, which will be sealed and positioned at the end of an aluminum pole, close to the core of a “swimming pool” reactor. Often samples are placed in plastic tubes and are carried in and out of a reactor by air pressure in a pneumatic tube system.
You carefully scrape off a small amount of material, weigh it on a sensitive balance, and put it into a short piece of pure quartz tubing. You do the same with an ordinary piece of silicon for comparison and then seal both tubes with an oxygen-gas torch. Although the tubes are both ¼ inch in diameter and about 1 inch long, the first tube is just slightly longer so you will be able to determine which is which after the irradiation.
Off it goes to the reactor in a carefully wrapped package along with instructions to irradiate the tubes for 12 hours in a neutron flux of about 10¹³ neutrons per square centimeter per second and to return them as quickly as possible after they are removed from the reactor.
The following week, the samples are delivered about 4 hours after they were removed from the reactor. Working quickly but carefully, you note that they are radioactive but easily handled by ordinary laboratory techniques. You break the quartz tubes one at a time and attach each of the two pieces of silicon to a card with self-sticking tape. Then you place each card, in turn, on a holder close to the gamma-ray detector for a period of 10 minutes. A spectrum, which is a graph of the quantity of radiation recorded in each increment of energy over the range observed for each of the samples, is plotted automatically at the end of the counting period and you may now compare the compositions of the two samples. (See the [figure on the next two pages].)
The two spectra are virtually identical except that the suspect sample has one obviously different peak in channel 157 and a somewhat smaller peak in channel 183. Referring to an energy calibration curve for the pulse height analyzer, you find that these channels correspond to 0.559 and 0.657 MeV respectively. A search of a table of nuclides, arranged by gamma-ray energy, reveals that this combination is emitted by arsenic-76, which would be the activation product for arsenic. Other data also indicate that for arsenic there should be a number of smaller peaks, including some corresponding to energies of 1.216, 1.228, 0.624, and 1.441 MeV. A closer look at the spectrum of the suspect sample reveals that these are also present.
Finally, noting that the half-life of arsenic-76 is approximately 27 hours, you wait a day and count the sample again in the same position as the previous count. A decrease in the heights of the 0.559 and 0.657 MeV peaks, by a little less than half in 24 hours, confirms that arsenic is the unusual element in this sample. It may not be the only impurity causing the peculiar behavior of this semiconductor, but it does seem a likely candidate.
The gamma-ray spectrum obtained after activation of a sample of “pure” silicon having “ordinary” properties of this type of semiconductor. Only very small quantities of various trace impurities are indicated.
The gamma-ray spectrum obtained after activation of a sample of silicon having “unusual” electrical properties. While most of the spectrum is identical with that obtained from the ordinary material, there is an interesting difference.
Using the equation given on [page 12], the approximate known values for half-life, sample weight, neutron flux, and periods of irradiation and decay after irradiation, and an estimated value for the number of arsenic-76 atoms measured by the gamma-ray spectrometer, you calculate that the arsenic content of the sample is approximately 44 parts per million (ppm). (See appendix.)
With this information as a starting point, you are now ready to proceed with further research on the properties of your semiconductor, e.g., if you double the concentration of arsenic, how will that affect its properties?